Coating composition, coating film, and method for producing coating film

ABSTRACT

To provide the water-repellent coating film having excellent transparency, abrasion resistance, weather resistance and water repellency, the method for producing the coating film, the multi-functional composite material provided with the coating film and the coating composition used therefor which has excellent dispersion stability. The coating composition comprises (A) the fluorine-containing ethylenic polymer prepared by copolymerizing a fluorine-containing ethylenic monomer having at least one functional group selected from hydroxyl, carboxyl, a carboxylic salt group, a carboxylic ester group and epoxy, (B-1) the metal oxide sol, and (C) the solvent.

This is the national stage of International Application No.PCT/JP97/02070, filed Jun. 16, 1997.

TECHNICAL FIELD

The present invention relates to a coating composition, a coating filmand a method for producing the coating film.

BACKGROUND ART

Hitherto various attempts have been studied to give water repellency towindow glasses and fender mirrors for the purpose to repel rain waterand to obtain clear view in rainy days.

For example, JP-A-4-124047, JP-A-4-325446 and JP-A-5-24885 disclosecoating of a silane compound containing a fluoroalkyl group R_(f) group)on a substrate such as glass. Also JP-A-4-359086, JP-A-5-170486 andJP-A-5-213633 disclose forming of a water-repellent oxide film bypartially hydrolyzing, with an acid, etc., a fluoroalkyl-containingsilane compound or a metal alkoxide mixed with a fluoroalkyl-containingsilane compound, condensation-polymerizing (to be sol) and then coatingon a glass substrate and baking (to be gel).

However the water-repellent glass obtained by the above-mentionedmethods has a problem that water-repellent groups are easy to distributein the outermost surface of the coating film and water-repellency islowered by abrasion. Further the fluoroalkyl-containing silane compoundand its condensate have insufficient heat resistance and weatherresistance, so that when used for a long period of time, they aredeteriorated and cannot maintain water-repellency.

Therefore in order to solve those problems, there have been investigatedvarious methods to obtain a water-repellent coating film by dispersingfluorine-containing resin particles having no functional group as awater-repelling component into a metal oxide obtained through so-calledsol-gel method. For example, in JP-A-5-51238, JP-A-6-329442,JP-A-6-340451, JP-A-7-102207 and JP-A-7-157335, it is disclosed that acoating solution is prepared by admixing particles (powder ordispersion) of water-repellent fluorine-containing resin such aspolytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene polymeror fluorine-containing acrylic resin to a sol solution prepared byhydrolyzing and condensating a metal alkoxide compound in a solvent suchas alcohol, and the coating solution is applied on a substrate such asglass and then baked (to be gel) to form a water-repellent coating filmthat the water-repellent particles are distributed in the sol-gel film.

However in those methods, though improvements of weather resistance andheat resistance can be expected, there are the following problems.

{circle around (1+L )} Dispersion stability of fluorine-containing resinparticles in the coating solution prepared by admixing thefluorine-containing resin particles to the sol solution is poor,sedimentation of the fluorine-containing resin particles easily occurs,and thus the coating film becomes turbid in white and transparencybecomes lowered significantly.

{circle around (2+L )} Even if the coating solution visually seems to bedispersed, when the solution is coated and concentrated in the coatingfilm during baking step, the fluorine-containing resin particles arecoagulated because of insufficient dispersion stability, and the coatingfilm becomes turbid in white and its transparency is lowered.

{circle around (3+L )} Since interfacial affinity between the metaloxide and the fluorine-containing resin particles is inherently low,dispersibility of the fluorine-containing resin particles in theobtained coating film is low, strength of the coating film is loweredand abrasion resistance of the coating film becomes low.

{circle around (4+L )} Since interfacial affinity between the metaloxide and the fluorine-containing resin particles in the obtainedcoating film is low, removal of the fluorine-containing resin particlesoccurs in the abrasion resistance test, and water-repellency is lowered.

As mentioned above, present situation is such that there have not yetbeen obtained a water-repellent coating film or water-repellent glasswhich is excellent in transparency and water-repellent durability suchas abrasion resistance and weather resistance, and a coating compositionwhich is used therefor and is excellent in dispersion stability.

An object of the present invention is to provide a multi-functionalcoating film being excellent in not only water-repellency andtransparency but also stain-proofing property, non-sticking property,sliding property (abrasion resistance) and weather resistance, a methodfor producing the coating film, a multi-functional composite materialprovided with the coating film, and a coating composition which is usedtherefor and is excellent in dispersion stability.

Further an object of the present invention is to provide compositematerials having water-repellency, stain-proofing property, non-stickingproperty, sliding property or weather resistance which are produced byapplying the mentioned coating film on a substrate.

Also an object of the present invention is to provide a compositematerial for cooking apparatuses and a composite material for building.

DISCLOSURE OF THE INVENTION

The present invention relates to a coating composition comprising

(A) a fluorine-containing ethylenic polymer having functional group(hereinafter also referred to as “fluorine-containing polymer (A) havingfunctional group”) prepared by copolymerizing a fluorine-containingethylenic monomer having functional group which has at least onefunctional group selected from the group consisting of hydroxyl,carboxyl, a carboxylic salt group, a carboxylic ester group or epoxy,

(B-1) a metal oxide sol, and

(C) a solvent.

Also in the present invention, it is preferable that the above-mentionedfluorine-containing polymer (A) having functional group is in the formof fine particles.

Also in the present invention, it is preferable that fine particles ofthe above-mentioned fluorine-containing polymer (A) having functionalgroup are water-repellent fine particles.

Also in the present invention, it is preferable that thefluorine-containing polymer (A) having functional group is afluorine-containing polymer having functional group which is prepared bycopolymerizing

(a) 0.05 to 50% by mole of at least one of fluorine-containing ethylenicmonomers having functional group and represented by the formula (1):

CX₂═CX¹-R_(f)-Y  (1)

herein Y is —CH₂OH, —COOH, a carboxylic salt group, a carboxylic estergroup or epoxy, X and X¹ are the same or different and each is hydrogenatom or fluorine atom, R_(f) is a divalent fluorine-containing alkylenegroup having 1 to 40 carbon atoms or a divalent fluorine-containingalkylene group having 1 to 40 carbon atoms and ether bond and

(b) 50 to 99.95% by mole of at least one of fluorine-containingethylenic monomers copolymerizable with the fluorine-containingethylenic monomer (a) having functional group.

Also in the present invention it is preferable that thefluorine-containing ethylenic monomer (a) having functional group is afluorine-containing ethylenic monomer having functional group andrepresented by the formula (2):

CH₂═CFCF₂—R_(f) ¹—Y¹  (2)

wherein Y¹ is —CH₂0H, -COOH, a carboxylic salt group, a carboxylic estergroup or epoxy, R_(f) ¹ is a divalent fluorine-containing alkylene grouphaving 1 to 39 carbon atoms or OR_(f) ², in which R_(f) ² is a divalentfluorine-containing alkylene group having 1 to 39 carbon atoms or adivalent fluorine-containing alkylene group having 1 to 39 carbon atomsand ether group.

Also in the present invention it is preferable that thefluorine-containing ethylenic monomer (b) is tetrafluoroethylene.

Also in the present invention it is preferable that thefluorine-containing ethylenic monomer (b) is a mixture of 85 to 99.7% bymole of tetrafluoroethylene and 0.3 to 15% by mole of a monomerrepresented by the formula (3):

 CF₂═CF—R³  (3)

wherein R_(f) ³ is CF₃ or OR_(f) ⁴, in which R_(f) ⁴ is a perfluoroalkylgroup having 1 to 5 carbon atoms.

Further the present invention relates to a metal oxide coating filmcomprising the above-mentioned metal oxide (B) and fine particles of thefluorine-containing polymer (A) having functional group, and containingthe fine particles in dispersed state.

Further the present invention relates to a metal oxide coating filmcomprising the above-mentioned metal oxide (B) and water-repellent fineparticles of the fluorine-containing polymer (A) having functionalgroup, and containing the water-repellent fine particles in dispersedstate.

Further the present invention relates to a method for producing acoating film by using (B-1) a metal oxide sol obtained from at least oneselected from the group consisting of a metal alkoxide, a metalacetylacetate, a metal carboxylate, a metal nitrate or a metal chlorideand an aqueous dispersion containing fine particles of theabove-mentioned fluorine-containing polymer (A) having functional groupobtained by emulsion polymerization; the method comprising the steps of

(1) preparing a coating solution by mixing the metal oxide sol (B-1) andthe aqueous dispersion,

(2) forming a coating film by applying the coating solution to asubstrate, and

(3) baking the coating film to obtain the film containing the fineparticles of the fluorine-containing polymer (A) having functional groupin dispersed state.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a diagrammatic perspective view of a sample used for anon-stickiness test in Example of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The coating composition of the present invention is the coatingcomposition comprising (A) the fluorine-containing ethylenic polymerhaving the specific functional group, (B-1) the metal oxide sol and (C)the solvent, and the important feature of the present invention is touse the fluorine-containing polymer (A) having functional group which isobtained by introducing the specific functional group.

The present inventors have found that, not only since dispersionstability of the fluorine-containing polymer (A) having functional groupin the metal oxide sol (B- 1) and the solvent (C) is enhanced remarkablybut also since the fluorine-containing ethylenic polymer (A) havingfunctional group is dispersed so uniformly in the coating film obtainedfrom the coating composition comprising the mentioned components, thecoating film is particularly good in transparency and is also excellentin water-repellency, stain-proofing property, non-sticking property,sliding property, weather resistance and heat resistance, and thus havecompleted the present invention.

Further the present inventors have found that even in case where thefine particles of the fluorine-containing polymer (A) having functionalgroup are used, the above-mentioned dispersion stability, transparency,water-repellency, stain-proofing property, non-sticking property,sliding property, weather resistance and heat resistance are moreexcellent, and that particularly when the water-repellent fine:particles of the fluorine-containing polymer (A) having functional groupare used, those characteristics are further enhanced, and particularlywater-repellency is significantly enhanced.

As compositions similar to the coating composition of the presentinvention, for example, JP-A-7-82520, WO94/06870 and JP-A-8-12921disclose coating compositions prepared by blending a hydrolyzable silanecompound with a polymer of a hydrocarbon vinyl ether having hydroxyl andfluorine-containing ethylene.

However the coating compositions disclosed in the mentioned publicationsare characterized in that after the coating, the fluorine-containingpolymer composes a matrix and the silane compound is phase-separatedtherefrom and spread in the surface region of the coating film. Namelythe inventions disclosed in the mentioned publications aim to make thecoating film surface hydrophilic by hydrolyzing the silane compound inthe surface region of the coating film to improve property forpreventing stain due to rain water, when used outdoors.

Accordingly those coating compositions cannot give a coating film havingthe excellent water-repellency, stain-proofing property, non-stickingproperty, sliding property, weather resistance and heat resistance ofthe present invention. Also the fluorine-containing polymers themselvesdisclosed in the mentioned publications have weather resistance but areinsufficient in water-repellency and heat resistance, and thus whenforming a coating film according to the sol-gel method of the presentinvention, thermal decomposition occurs, for example, at the time ofbaking step, which results in poor appearance of the coating film andlowering of the inherent characteristics of the fluorine-containingresin.

On the other hand since the fluorine-containing polymer (A) havingfunctional group in the coating composition of the present invention isa polymer obtained particularly by copolymerizing thefluorine-containing ethylenic monomer having functional group and thefluorine-containing ethylenic monomer which does not have theabove-mentioned functional group, the polymer itself has a largefluorine content and is excellent in water-repellency, stain-proofingproperty, non-sticking property, sliding property, weather resistanceand heat resistance. Thus the polymer is not thermally decomposed at thebaking step and can give a metal oxide coating film having excellenttransparency and water-repellency.

The specific functional group of the fluorine-containing polymer (A)having functional group which can be used in the coating composition ofthe present invention is at least one of hydroxyl, carboxyl, acarboxylic salt group, a carboxylic ester group and epoxy, and isselectively and optionally used depending on purposes and applications,namely kind of the metal oxide (B), kind of a starting material such asmetal alkoxide used when preparing the metal oxide sol (B-1) and kind ofa substrate surface. From the viewpoints of dispersion stability of thecoating composition and heat resistance at baking, hydroxyl is mostpreferable.

Example of the fluorine-containing polymer (A) used in the coatingcomposition of the present invention is a fluorine-containing polymerhaving functional group which is prepared by copolymerizing (a) 0.05 to50% by mole of at least one of fluorine-containing ethylenic monomershaving functional group and represented by the formula (1):

 CX₂═CX¹—R_(f)—Y  (1)

wherein Y is —CH₂OH, —COOH, a carboxylic salt group, a carboxylic estergroup or epoxy, X and X¹ are the same or different and each is hydrogenatom or fluorine atom, R_(f) is a divalent fluorine-containing alkylenegroup having 1 to 40 carbon atoms or a divalent fluorine-containingalkylene group having ether bond and 1 to 40 carbon atoms, and

(b) 50 to 99.95% by mole of at least one of fluorine-containingethylenic monomers copolymerizable with the fluorine-containingethylenic monomer (a) having functional group. The obtainedfluorine-containing polymer having functional group is excellent in heatresistance, weather resistance and water-repellency.

Examples of the fluorine-containing ethylenic monomer (a) havingfunctional group are monomers represented by the formula (4):

CF₂═CF—R_(f) ⁵—Y  (4)

wherein Y is the same as Y in the formula (1), R_(f) ⁵ is a divalentfluorine-containing alkylene group having 1 to 40 carbon atoms or OR_(f)⁶, in which R_(f) ⁶ is a divalent fluorine-containing alkylene grouphaving 1 to 40 carbon atoms or a divalent fluorine-containing alkylenegroup having ether bond and 1 to 40 carbon atoms, the formula (5):

CF₂═CFCF₂—OR_(f) ⁷—Y  (5)

wherein Y is the same as Y in the formula (1), R_(f) ⁷ is a divalentfluorine-containing alkylene group having 1 to 39 carbon atoms or adivalent fluorine-containing alkylene group having ether bond and 1 to39 carbon atoms, the formula (2):

CH₂═CFCF₂—R_(f) ¹—Y¹  (2)

herein Y¹ is the same as Y in the formula (1), 1 is a divalentfluorine-containing alkylene group having 1 to 39 carbon atoms or OR_(f)², in which R_(f) ² is a divalent fluorine-containing alkylene grouphaving 1 to 39 carbon toms or a divalent alkylene group having etherbond and 1 to 39 carbon atoms, the formula (6):

CH₂═CH—R_(f) ⁸—Y  (6)

wherein Y is the same as Y in the formula (1), R_(f) ⁸ is a divalentfluorine-containing alkylene group having 1 to 40 carbon atoms, and thelike.

The fluorine-containing ethylenic monomers having functional group whichare represented by the formulae (2) and (4) to (6) are preferable fromthe points that copolymerizability with the fluorine-containingethylenic monomer (b) is relatively good and that heat resistance andwater-repellency of the polymer obtained by the copolymerization is notlowered remarkably.

Among them, from the viewpoints of copolymerizability with otherfluorine-containing ethylenic monomer and heat resistance of theobtained polymer, the monomers represented by the formulae (2) and (4)are preferable, and the monomer represented by the formula (2) isparticularly preferable.

Examples of the fluorine-containing ethylenic monomer having sectionalgroup and represented by the formula (4) are:

CF₂═CFOCF₂CF₂CH₂OH, CF₂═CFO(CF₂)₃COOH,

CF₂═CFOCF₂CF₂COOCH₃,

 CF₂═CFCF₂COOH, CF₂═CFCF₂CH₂OH,

and the like.

Examples of the fluorine-containing ethylenic monomer having functionalgroup and represented by the formula (5) are:

CF₂═CFCF₂OCF₂CF₂CF₂COOH,

CF₂═CFCF₂OCF₂CF₂CF₂CH₂OH,

and the like.

Examples of the fluorine-containing ethylenic monomer having functionalgroup and represented by the formula (2) are:

CH₂═CFCF₂CF₂CH₂CH₂OH, CH₂═CFCF₂CF₂COOH,

and the like.

Examples of the fluorine-containing ethylenic monomer having functionalgroup and represented by the formula (6) are:

CH₂═CHCF₂CF₂CH₂CH₂COOH,

 CH₂═CHCF₂₄CH₂CH₂CH₂OH,

CH₂═CHCF₂₆CH₂CH₂COOCH₃,

and the like.

In addition, there are

and the like.

The ethylenic monomer copolymerizable with the fluorine-containingethylenic monomer (a) having functional group can be optionally selectedfrom known monomers. From the viewpoint of giving water-repellency,stain-proofing property, non-sticking property, sliding property,weather resistance, chemical resistance and heat resistance to thepolymer, the copolymerizable ethylenic monomer is selected from thefluorine-containing ethylenic monomers (b).

Examples of the fluorine-containing ethylenic monomer (b) aretetrafluoroethylene, a monomer represented by the formula (3):

CF₂═CF-R_(f) ³   (3)

wherein R_(f) ³ is CF₃ or OR_(f) ⁴, in which R_(f) ⁴ is a perfluoroalkylgroup having 1 to 5 carbon atoms, hexafluoropropylene,chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride,perfluoro(alkyl vinyl ethers), hexafluoroisobutene,

CH₂═CFCF²_(n)X², CH₂═CHCF₂_(n)X²,

wherein both of X² are selected from hydrogen atom, fluorine atom andchlorine atom, both of n are an integer of 1 to 5, and the like.

In addition to the fluorine-containing ethylenic monomer (a) havingfunctional group and the fluorine-containing ethylenic monomer (b), anethylenic monomer having no fluorine atom may be added in the range ofnot lowering water-repellency, heat resistance and non-stickingproperty. In that case, it is preferable that the ethylenic monomerhaving no fluorine atom is selected from ethylenic monomers having notmore than 5 carbon atoms in order not to lower water-repellency and heatresistance. Examples of such an ethylenic monomer are ethylene,propylene, 1-butene, 2-butene, and the like.

A content of the fluorine-containing ethylenic monomer (a) havingfunctional group in the fluorine-containing ethylenic polymer (A) havingfunctional group which is used in the coating composition of the presentinvention can be optionally selected depending on kinds of the metaloxide sol (B-1) in the composition and the metal oxide (B) forming thecoating film, a proportion of the fluorine-containing polymer (A) havingfunctional group to the metal oxide sol (B-1), a solid content, apercentage of the fluorine-containing polymer (A) having functionalgroup in the coating film, and further depending on purposes andapplications. The content of the fluorine-containing ethylenic monomer(a) having functional group is preferably from 0.05 to 50% by mole, morepreferably from 0.1 to 20% by mole, particularly preferably from 0.1 to10% by mole.

When the content of the fluorine-containing ethylenic monomer (a) havingfunctional group is less than 0.05% by mole, dispersion stability of thecoating composition becomes insufficient, the composition isprecipitated and the coating film is tinged with white. Also interfacialadhesion between the metal oxide in the coating film and thefluorine-containing polymer (A) having functional group which isdispersed in the coating film becomes insufficient, and thefluorine-containing polymer (A) having functional group is removed byfriction, etc., and thus water-repellency is lowered.

On the contrary when the content of the fluorine-containing ethylenicmonomer (a) having functional group exceeds 50% by mole, inherentwater-repellency of the fluorine-containing polymer (A) havingfunctional group is lost, its heat resistance is lowered, and whenbaking at high temperature, thermal decomposition, coating film defectssuch as coloring, foaming and pin hole, and lowering of water-repellencyeasily occur.

Examples of the preferred fluorine-containing ethylenic polymer (A)having functional group used in the coating composition of the presentinvention are as follows.

(I) A polymer comprising 0.05 to 50% by mole of the fluorine-containingethylenic monomer (a) having functional group and 50 to 99.95% by moleof tetrafluoroethylene. For example, there is polytetrafluoroethylenehaving functional group (reactive PTFE).

(II) A polymer comprising 0.05 to 50% by mole of the fluorine-containingethylenic monomer (a) having functional group based on the total amountof monomers, and based on the total amount of monomers except themonomer (a), 85 to 99.7% by mole of tetrafluoroethylene and 0.3 to 15%by mole of a monomer represented by the formula (3):

CF₂═CF—R³  (3)

wherein R_(f) ³ is CF₃ or OR_(f) ⁴, in which R_(f) ⁴ is a perfluoroalkylgroup having 1 to 5 carbon atoms. For example, there is atetralluoroethylene-perfluoro(allyl vinyl ether) polymer havingfunctional group (reactive PFA) or atetrafluoroethylene-hexafluoropropylene polymer having functional group(reactive FEP).

(III) A polymer comprising 0.05 to 50% by mole of thefluorine-containing ethylenic monomer (a) having functional group basedon the total amount of monomers, and based on the total amount ofmonomers except the monomer (a), 40 to 80% by mole oftetrafluoroethylene, 20 to 60% by mole of ethylene and 0 to 15% by moleof other copolymerizable monomer. For example, there is anethylene-tetrafluoroethylene polymer having functional group (reactiveETFE).

Those fluorine-containing polymers (A) having functional group have ahigh melting point of not less than 200° C., and are preferable from thepoint that when producing a coating film which comprises thefluorine-containing polymer (A) having functional group and the metaloxide (B) and contains fine particles of the fluorine-containing polymer(A) having functional group in dispersed state, the polymer (A) does notmelt even at baking at high temperature and can be maintained in theform of fine particles in the coating film.

The fluorine-containing ethylenic polymer (A) having functional groupwhich can be used in the present invention can be prepared bycopolymerizing the fluorine-containing ethylenic monomer (a) havingfunctional group and the ethylenic monomer (b) through knownpolymerization methods. Among them, radical copolymerization method ismainly used. Namely means for initiating the polymerization is notparticularly limited if the polymerization advances radically. Forexample, the polymerization is initiated by an organic or inorganicradical polymerization initiator, heat, light, ionizing radiation, etc.The polymerization can be carried out by solution polymerization, bulkpolymerization, suspension polymerization, emulsion polymerization, orthe like. A molecular weight of the polymer (A) is regulated by aconcentration of the monomers used in the polymerization, aconcentration of the initiator, and a concentration and temperature of achain transfer agent. Amounts of components of the prepared polymer canbe regulated by amounts of monomers used.

Also the present invention relates to the metal oxide coating film whichcomprises the matrix metal oxide (B) and fine particles of thefluorine-containing ethylenic polymer (A) having functional group andcontains the above-mentioned fine particles in dispersed state.

The metal oxide (B) which forms a matrix in the coating film obtained inthe present invention is preferably one which is obtained by hydrolyzingand polycondensating, for example, an organic compound or inorganiccompound of metal as a starting material in the solvent (C) mentionedhereinafter, or the like.

As the so-obtained metal oxide (B), there can be used various onesdepending on purposes and applications. For example, there are oxides ofmetals (M) in the Periodic Table of Elements such as:

Ia group: Li, Na,

Ib group: Cu,

IIa group: Ca, Sr, Ba,

IIb group: Zn,

IIIa group: Y,

IIIb group: B, Al, Ga,

IVa group: Ti, Zr,

IVb group: Si, Ge,

Va group: V, Ta,

Vb group: P, Sb,

VIa group: W,

Lanthanide group: La, Nd,

and the like. Also there can be used metals having two or more valences,namely metal oxides (R-MO) in which an organic group (R) such as analkylene group having a functional group, for example, alkyl,fluorine-containing alkyl, amino, epoxy, hydroxyl, etc. is directlybonded to metal (M). More concrete examples of the metal oxide (B) arementioned later.

As the above-mentioned metal (M), various ones can be selected dependingon purposes and applications. Paticularly preferable is metal selectedfrom Si, Al, Ti and Zr from the point of making it possible to form atransparent coating film having high hardness and excellent durability.

In the present invention, a proportion (A)/ (B) (volume ratio) of thefluorine-containing ethylenic polymer (A) having functional group to themetal oxide (B) in the coating film formed on a surface of a substratementioned later is preferably 1 to 85/99 to 15, particularly preferably5 to 75/25 to 95 from the viewpoints of transparency and strength of thecoating film. When an amount of the fluorine-containing polymer (A)having functional group is too much, transparency of the coating film islowered and the coating film becomes fragile. On the contrary, when toosmall, excellent inherent characteristics of the fluorine-containingresin such as water-repellency, non-sticking property and stain-proofingproperty are lowered.

The coating film of the present invention is a metal oxide coating filmobtained by so-called sol-gel method, and can be formed by applying, ona substrate, the coating composition comprising fine particles of thefluorine-containing ethylenic polymer (A) having functional group, themetal oxide sol (B-1) (hydrolysate or lower molecular weight condensatebefore gelling) which is a precursor of the metal oxide (B) and thesolvent (C).

Accordingly the present invention also relates to such a coatingcomposition.

As the solvent (C) which can be used in the coating composition of thepresent invention, there are various solvents. From the point that ahomogeneous solution of the metal oxide sol (B-1) can be prepared, thereare mainly used the solvent selected from alcohols such as methanol,ethanol, propanol, isopropanol, butanol and isobutanol and water foraccelerating the hydrolyzing.

When the metal compound insoluble in those solvents is used as astarting material for the metal oxide sol (B-1) (namely metal oxidecoating film), ethylene glycol, ethylene oxide, triethanolamine, xyleneor the like may be used. Also for preventing cracking of the coatingfilm, there may be used formamide, dimethylformamide, dioxane, oxalicacid and other solvents having high boiling point.

In the coating composition of the present invention, a proportion of thefluorine-containing ethylenic polymer (A) having functional group, metaloxide sol (B-1) and the solvent (C) can be selected optionally dependingon purposes and applications. Amounts of the fluorine-containing polymer(A) having functional group and metal oxide sol (B-1) are preferably 1to 85% by weight and 15 to 99% by weight, respectively based on thetotal amount of the polymer (A) and the metal oxide sol (B-1), morepreferably 10 to 75% by weight and 25 to 90% by weight, respectively.

Also the total amount of the fluorine-containing polymer (A) havingfunctional group and metal oxide sol (B-1) in the whole composition isfrom 0.1 to 70% by weight, preferably from 0.5 to 50% by weight.

In the coating composition of the present invention, thefluorine-containing ethylenic polymer (A) having functional group ispreferably in the form of fine particles, and after coated, is dispersedin the form of fine particles in the metal oxide coating film and canprovide the coating film having particularly excellent abrasionresistance and water-repellency.

An average particle size of fine particles of the fluorine-containingethylenic polymer (A) having functional group is from about 0.01 μm toabout 1.0 μm, preferably not more than 0.6 μm. In this range,particularly when transparency is required, the average particle size ispreferably not more than 0.4 μm. Also when dispersion stability andstorage stability of the coating composition and transparency of thecoating film are required, the average particle size is most preferablynot more than 0.2 μm.

The fine particles of the fluorine-containing polymer (A) havingfunctional group are prepared by various methods, and are preferablyprepared by emulsion polymerization from the point that the particlesize can be regulated to be fine and uniform. In that case, the coatingcomposition of the present invention can be prepared by directly mixingan aqueous dispersion of fine particles of the fluorine-containingpolymer (A) having functional group obtained by emulsion polymerizationwith a previously prepared solution of the metal oxide sol (B-1) or byhydrolyzing and poly-condensating the metal compound in a solventcontaining an aqueous dispersion of fine particles of thefluorine-containing polymer (A) having functional group.

To the coating composition of the present invention can be addedadditives, for example, a surfactant, pigment, dye, thickener, etc.

The coating film of the present invention is formed by applying thecoating composition (solution in the form of sol) containing the fineparticles of the fluorine-containing ethylenic polymer (A) havingfunctional group and metal oxide sol (B-1) on various substratesmentioned later of ceramics such as glass and pottery, metal, syntheticresin, etc. Then by baking (gelling) (namely sol-gel method) the coatingfilm, the poly-condensation of the metal oxide sol (B-1) furtheradvances and the hard coating film of the metal oxide (B) having highstrength is formed. The obtained coating film of the metal oxidecontains the uniformly dispersed fluorine-containing polymer (A) in theform of particles.

Since the fine particles of the fluorine-containing polymer (A) areuniformly distributed up to the inside of the metal oxide coating filmof the present invention, even if the surface of the coating film isabraded and shaved off, excellent characteristics (water-repellency,etc.) of the fluorine-containing resin are exhibited even in the coatingfilm and are not lowered.

The mentioned baking is preferably carried out at a temperature of notmore than the melting point of the fluorine-containing polymer (A) inorder to uniformly disperse the particles thereof in the metal oxidecoating film. However when a polymer which has a high melt viscosity andis not melted (for example, PTFE, etc.) is used in the form of fineparticles, the baking can be carried out at a temperature higher thanthe melting point unless the temperature exceeds the thermaldecomposition temperature of the fluorine-containing polymer (A).

A thickness of the metal oxide coating film of the present inventionvaries depending on purposes and applications, and is from 0.01 to 100μm.

Further the present invention relates to a method for producing thementioned coating film. The coating film can be produced, for example,by using the aqueous dispersion containing fine particles of thefluorine-containing polymer (A) having functional group prepared byemulsion polymerization and the metal oxide sol (B-1) obtained byhydrolyzation and condensation reaction of at least one startingmaterial selected from the group consisting of a metal alkoxide, metalacetylacetate, metal carboxylate, metal nitrate and metal chloride. Themethod comprises the steps of:

(1) preparing a coating solution by mixing the metal oxide sol (B-1) andthe aqueous dispersion,

(2) forming the coating film by applying the coating solution to asubstrate, and

(3) baking the coating film to obtain the film containing the fineparticles of the fluorine-containing polymer (A) having functional groupin dispersed state.

(Preparation of solution of metal oxide sol)

The above-mentioned metal oxide sol (B-1) can be prepared by hydrolyzingand poly-condensating a corresponding metal alkoxide, metalacetylacetate, metal carboxylate, metal nitrate, metal chloride or amixture of two or more thereof.

Among them, metal alkoxide is preferred since it is highly reactive andeasily forms a polymer (metal oxide) having metal-oxygen bond by thehydrolyzation and poly-condensation reaction.

In case where no proper metal alkoxide is available, namely whensynthesizing of the metal alkoxide is difficult or when the metalalkoxide is insoluble in commonly used solvents such as water andalcohol (for example, copper alkoxide, etc.), a carboxylate such asmetal acetylacetate or metal acetate, an oxylate, etc. can be used.

Further in case where proper metal alkoxide and other organic metalcompound are not available, inorganic metal compounds such as metalnitrate, metal chloride and metal oxide can be used.

The metal alkoxide is a compound represented by M(OR)n, in which M ismetal, R is alkyl, n is a figure corresponding to a valence of themetal. In general, the metal M can be optionally selected depending onpurposes and applications of a finally obtained coating film containinga corresponding metal oxide. The alkyl R can be selected depending onpurposes in consideration of solubility and insolubility in a solvent,hydrolyzability, poly-condensation reactivity, etc.

Examples of the metal alkoxide are, for instance, LiOCH₃, NaOCH₃,Cu(OCH₃)₂, Ca(OCH₃)₂, Sr(OC₂H₅)₂, Ba(OC₂H₅)₂, Zn(OC₂H₆)₂, Y(OC₄H₉)₃,B(OCH₃)₃, Al(OCH₃)₃, Al(OC₂H₅)₃, Al(iso-OC₃H₇)₃, Al(OC₄H₉)₃, Ga(OC₂H₅)₃,Ti(OCH₃)₄, Ti(OC₂H₅)₄, Ti(iso-OC₃H₇)₄, Ti(OC₄H₉)₄, Zr(OCH₃)₄,Zr(OC₂H₅)₄, Zr(OC₃H₇)₄, Zr(OC₄H₉)₄, Si(OCH₃)₄, Si(OC₂H₅)₄,Si(iso-OC₃H₇)₄, Si(t-OC₄H₉)₄, Ge(OC₂H₅)₄, Pb(OC₄H₉)₄, P(OCH₃)₃,Sb(OC₂H₅)₃, VO(OC₂H₅)₃, Ta(OC₃H₇)₅, W(OC₂H₅)₆, La(OC₃H₇)₃, Nb(OC₂H₅)₃,La[Al(iso-OC₃H₇)₄]₃, Mg[Al(iso-OC₃H₇)₄]₂, Mg[Al(sec-OC₄H₉)₄]₂,Ni[Al(iso-OC₃H₇)₄]₂, (C₃H₇O)₂Zr[Al(OC₃H₇)₄]₂, Ba[Zr₂(OC₂H₅)₉]₂, and thelike.

As the metal alkoxide, there can be used not only a compound prepared bybonding only an alkoxyl group to metal but also a compound obtained bysubstituting a part of an alkoxyl group with an alkyl group such asmethyl or ethyl, a compound obtained by substituting a part of analkoxyl group with a fluorine-containing alkyl group, and a compoundobtained by substituting a part of an alkoxyl group with an alkylenegroup, having a functional group such as amino, epoxy, hydroxyl ormercapto.

Examples of those compounds are

CH₃SiOC₂H₅)₃, C₂H₅SiOC₂H₅)₂,

CF₃CF₂)₅CH₂CH₂Si(OCH₃)₃,

CF₃CF₂)₇CH₂CH₂Si(OCH₃)₃,

H₂N—CH₂₃ Si(OCH₃)₃, HOCH₂₃Si(OCH₃)₃,

HSCH₂₃Si(OCH₃)₃,

and the like.

Examples of other organic metal compound are metal acetylacetates, forinstance, Zr(COCH₂CH₃)₄, In(COCH₂COCH₃)₃ and Zn(COCH₂COCH₃)₂, metalcarboxylates, for instance, Pb(CH₃COO)₂, Y(C₁₇H₃₅COO)₃ and Ba(HCOO)₂,and the like.

Examples of the inorganic metal compound are metal nitrates, forinstance, Y(NO₃)₃•6H₂O and Ni(NO₃)₂•3H₂O, metal oxychlorides, forinstance, ZrOCl₂ and AlOCl, metal chlorides, for instance, TiCl₄, andthe like. Also it is possible to make sol again and carry out sol-gelmethod by using a metal compound such as a fumed silica.

In preparing a solution of the metal oxide sol (B-1), at first a metalcompound corresponding to metal of a desired metal oxide is selectedfrom the above-mentioned compounds and then dissolved in an alcoholicsolvent. In that case, it is desirable that the metal compound isdissolved in the solvent uniformly, and it is preferable to select ametal compound which dissolves in the solvent.

By adding water and acid or alkali as a catalyst to the solution ofmetal compound, hydrolyzation and poly-condensation occur and particlesof the metal compound are generated, thus giving a solution of metaloxide sol (B-1).

Examples of the acid which can be used generally as the catalyst are,for instance, hydrochloric acid, sulfuric acid, nitric acid, aceticacid, hydrofluoric acid, etc. For the alkali as the catalyst, there canbe used preferably, for example, an ammonia which can be removed byevaporation after the treatment.

A reaction temperature when preparing a solution of the metal oxide solvaries depending on kind of metal, kind of metal compound used, degreeof polymerization of a desired sol, etc. The reaction temperature is ingeneral from room temperature to 100° C., preferably from roomtemperature to about 80° C. A solid content is preferably from 0.5 to50% by weight.

As the case demands, it is possible to prepare the metal oxide sol (B-1)by carrying out the hydrolyzation and poly-condensation slowly withmoisture in the air without adding water and catalyst. (Preparation ofaqueous dispersion of fluorine-containing polymer (A) having functionalgroup)

The fine particles of the fluorine-containing polymer (A) havingfunctional group which are mixed with the metal oxide sol (B-1) can beprepared by various methods.

For example, there are:

(i) a method for finely pulverizing a powder of the fluorine-containingpolymer (A) having functional group obtained by suspensionpolymerization, etc., adding the finely pulverized powder together witha surfactant, etc. into a solution of the metal oxide sol (B-1) and thenmixing uniformly (In this case, a coating solution mentioned later isgenerated at the same time as in the dispersion),

and

(ii) a method for preparing an aqueous dispersion of thefluorine-containing polymer (A) having functional group at the same timeof the polymerization by emulsion polymerization (In this case, it ispossible to mix directly with the solution of the metal oxide sol(B-1)). From the viewpoints of productivity and quality (making particlesize smaller and uniform), it is preferable to prepare an aqueousdispersion by emulsion polymerization and mix the aqueous dispersion asit is directly with the solution of the metal oxide sol (B-1). Theaqueous dispersion of fine particles of the fluorine-containing polymer(A) having functional group usually has 1 to 70% by weight, preferably 5to 50% by weight of solid content.

(Step for preparing coating solution)

As the method for preparing a solution (coating solution) of the metaloxide sol (B-1) containing fine particles of the fluorine-containingpolymer (A) having functional group, there can be adopted any of:

(iii) a method for preparing a coating solution by hydrolyzing andpoly-condensating a metal compound in an alcohol solution containing anaqueous dispersion of fine particles of the fluorine-containing polymer(A) having functional group to form the metal oxide sol (B-1), and

(iv) a method for preparing a coating solution by mixing an aqueousdispersion of fine particles of the fluorine-containing polymer (A)having functional group with a solution of the metal oxide sol (B-1)previously prepared by hydrolyzation and poly-condensation.

The present inventors have found that the dispersion of fine particlesof the fluorine-containing polymer (A) having functional group has highdispersion stability to an alcoholic solvent or other non-aqueoussolvent by an effect of a functional group which the polymer possessesand therefore even in the step of preparing the coating solution by anyof the above-mentioned methods, neither sedimentation nor precipitationof the fine particles occurs. Also prior to the coating, a solid contentin the coating solution may be adjusted depending on a desired thicknessand kind and shape of a substrate, and a viscosity of the coatingsolution may be adjusted by adding a thickener or by other method.

(Coating step)

Depending on purposes and applications, the coating solution can beapplied to various substrates of not only glass and metal but alsoresin, ceramic, etc. mentioned later.

The coating can be carried out by known methods such as dip coating,spin coating, spray coating, brush coating and roll coating.

(Baking step)

The coating film is baked to form a film containing fine particles ofthe fluorine-containing polymer (A) having functional group in dispersedstate. In usual case, prior to the baking, drying for removing water andsolvent is carried out at a temperature of from room temperature to 100°C., preferably from room temperature to about 80° C.

The baking temperature varies depending on purpose, application and kindof the fluorine-containing polymer (A) having functional group. Thebaking temperature is not less than 100° C. and lower than thedecomposition temperature of the fluorine-containing polymer (A),preferably not less than 150° C. and lower than the melting point of thefluorine-containing polymer (A) having functional group. When the bakingtemperature is not more than 100° C., since the condensationpolymerization (gelling) of the metal oxide does not advancesufficiently, crosslinking is insufficient and a coating film havinghigh hardness and strength cannot be obtained.

Also when the baking temperature exceeds the decomposition temperatureof the fluorine-containing polymer (A), not only foaming and coloringoccur but also excellent properties of the fluorine-containing resinsuch as water-repellency are lost.

In order to disperse the fluorine-containing polymer (A) havingfunctional group in the form of particles in the coating film comprisingthe metal oxide (B) and fine particles of the fluorine-containingpolymer (A), it is preferable to carry out the baking at a temperatureof not more than the melting point of the fluorine-containing polymer(A). However in case where fine particles of a polymer which has a highmelt viscosity and is not melted (for example, PTFE, etc.) are used, thebaking can be carried out even at a temperature of not less than themelting point unless the temperature exceeds the decompositiontemperature of the fluorine-containing polymer (A).

In the coating composition of the present invention comprising fineparticles of the fluorine-containing polymer (A) having functionalgroup, metal oxide (B) and solvent (C), since the fine particles havewater-repellency, stain-proofing property, non-sticking property,sliding property, weather resistance and heat resistance, amulti-functional coating composition can be obtained, and further bycoating the composition on a substrate and then baking, a coating filmexcellent particularly in water-repellency, stain-proofing property,non-sticking property, sliding property, weather resistance and heatresistance can be formed on the substrate.

Examples of the preferred fine particles of the fluorine-containingpolymer (A) having functional group are in general those of a polymer,in which a contact angle of water of the fluorine-containing polymer (A)itself is not less than 80 degrees, particularly not less than 95degrees. Also a fluorine-containing polymer which is neither thermallydecomposed nor melted in the baking step at high temperature ispreferable in order to maintain the form of fine particles of thefluorine-containing polymer (A) in the coating film comprising the metaloxide (B) and fine particles of the fluorine-containing polymer (A).Particularly a polymer having a melting point of not less than 150° C.,preferably not less than 200° C., particularly preferably not less than250° C. is used.

Examples of the particularly preferable fluorine-containing polymer (A)giving a coating film excellent in water-repellency, stain-proofingproperty, non-sticking property, sliding property, weather resistanceand heat resistance are the above-mentioned polymers (I), (II), (III)and the like.

Also it is particularly preferable that a content of thefluorine-containing ethylenic monomer (a) having functional group inthose fluorine-containing polymers (A) is from 0.1 to 10% by mole.

In the present invention, since the coating film has water-repellency,stain-proofing property, non-sticking property, sliding property,weather resistance and heat resistance, a multi-functional compositematerial comprising the coating film and a substrate can be obtained.Therefore the present invention relates to such a multi-functionalcomposite material.

Examples of the substrate on which the coating film of the presentinvention can be formed are a metallic substrate, non-metallic inorganicsubstrate, synthetic resin substrate, and the like.

Metals of the metallic substrate encompass metal, alloys of two or moremetals, metal oxide, metal hydroxide, metal salts such as carbonate andsulfate, etc. Among them, metal, metal oxide and alloys are morepreferable from the viewpoint of adhesive property.

Examples of the metallic substrate are metals and metal compounds ofaluminum, iron, nickel, titanium, molybdenum, magnesium, manganese,copper, silver, lead, tin, chromium, beryllium, tungsten and cobalt,alloys of two or more thereof, etc.

Examples of the alloys are alloy steels such as carbon steel, Ni steel,Cr steel, Ni-Cr steel, Cr-Mo steel, stainless steel, silicon steel andPermalloy; aluminum alloys such as Al-Cl, Al-Mg, Al-Si, Al-Cu-Ni-Mg andAl-Si-Cu-Ni-Mg; copper alloys such as brass, bronze, silicon bronze,silicon brass, nickel silver and nickel bronze; nickel alloys such asnickel manganese (D nickel), nickel-aluminum (Z nickel), nickel-silicon,Monel metal, Constantan, nichrome Inconel and Hastelloy; and the like.

Further as the aluminum-based metal, there can be used pure aluminum;aluminum oxide; and aluminum alloys for casting and expanding such asAl-Cu, Al-Si, Al-Mg, Al-Cu-Ni-Mg, Al-Si-Cu-Ni-Mg alloys, high tensilealuminum alloy and corrosion resistant aluminum alloy.

Also as the iron-based metals, there can be used pure iron, iron oxide,carbon steel, Ni steel, Cr steel, Ni-Cr steel, Cr-Mo steel, Ni-Cr-Mosteel, stainless steel, silicon steel, Permalloy, non-magnetic steel,magnet steel, cast steel, etc.

Also the coating composition of the present invention can be adhered toa substrate which was subjected to, for the purpose of preventingcorrosion of metal, coating of other metal by electroplating, hot.dipping, chromatizing, siliconizing, colorizing, sheradizing, metalspraying, etc.; forming a phosphate film by phosphatization; formingmetal oxide by anodizing or heat-oxidizing; or electrochemical corrosionprevention.

Further for the purpose of enhancing adhesion to a coating film, thesurface of metallic substrate may be subjected to chemical preparationwith a phosphoric acid, sulfuric acid, chromic acid, oxalic acid, etc.,or may be subjected to surface roughening by sand blasting, shotblasting, grit blasting, honing, paper scratching, wire scratching, hairline finishing, etc. For the purpose of exhibiting clear surface patternof the substrate, the metal surface may be subjected to coloring,printing, etching, etc.

In case of the above-mentioned aluminum or aluminum alloy substrate, inorder to enhance corrosion resistance, surface hardness and adhesiveproperty of the substrate, it is possible to form an oxide film(alumite) on the substrate by anodizing with caustic soda, oxalic acid,sulfuric acid or chromic acid and also use the aluminum or aluminumalloy substrate subjected to other surface treatments mentioned above.

Further there may be used a substrate plated, on its surface, othermetal as mentioned above, for example, steel plate subjected to hot-dipzinc-plating, hot-dip zinc alloy plating, aluminum plating, zinc-nickelplating, zinc-aluminum plating, or the like; a substrate coated withother metal by diffusion coating or thermal spraying; a substrate, onwhich an oxide film is formed by chemical conversion treatment withchromic acid or phosphoric acid or heat-treatment; a substrate subjectedto electric corrosion preventing treatment (for example, galvanizedsteel plate); or the like.

Examples of the non-metallic inorganic substrate are, for instance,glass, pottery, porcelain, etc.

Components of glass are not particularly limited. Examples are silicaglass, lead glass, alkali glass, non-alkali glass, etc.

Examples of the synthetic resin substrate are, for instance, an acrylicresin, polycarbonate, artificial marble, heat resistant engineeringplastic, thermosetting resin, etc.

The above-mentioned substrate in the present invention may be in theform of sheet, film, tube, pipe, plate or bar or in the other irregularform. However it is preferable that the form of the substrate is thesame as or similar to a form of a finished product from the viewpoint ofprocessability.

The multi-functional composite material of the present inventionobtained in the above-mentioned manner can be used as variousmulti-functional composite materials depending on applications andcomposite materials for specific products in various fields since it hasnot only water-repellency but also excellent stain-proofing property,non-sticking property, sliding property, weather resistance and heatresistance and further since fine particles of the fluorine-containingethylenic polymer (A) having functional group are uniformly dispersed inthe coating film comprising the matrix metal oxide (B) because of theirexcellent interfacial adhesion and the coating film has enough hardness,transparency and adhesive property. Explained hereinafter areembodiments of the multi-functional composite materials of the presentinvention, but the present invention is not limited to them.

EMBODIMENT 1 (Water-repellent composite material)

Cooking apparatuses and tablewares which are used in a watery place, forexample, in a kitchen and get wet at the time of washing have beenhitherto required to have water-repellency so as to be easily dried,namely use of water-repellent material has been required. Also in thefield of automobiles, use of water-repellent material on a windshieldand fender mirror of cars has been required in order to repel rain waterand make field of view good in rainy days.

Most generally available water-repellent materials arefluorine-containing materials, particularly fluorine-containing resinswhich are actually used.

However the above-mentioned fluorine-containing resins have substantiveproblem that due to their excellent non-sticking property, adhesion to asubstrate such as metal or glass is not sufficient.

In order to comply with such requirements, for a composite materialused, for example, for cooking apparatuses, etc., a fluorine-containingpolymer which is excellent in heat resistance, chemical resistance,corrosion resistance, weather resistance, surface properties(non-sticking property and low friction property) and electricinsulating property has been used. Such a composite material is used ona heating surface of cooking apparatuses such as rice cooker or electricgriddle. However the fluorine-containing polymer has insufficientadhesion to metal surface due to its excellent non-sticking property.Therefore it is necessary to (1) use an adhesive or (2) carry out, on asurface of a substrate, sand-blasting or etching by electrochemicalmethod to make the surface rough for adhering by anchor effect.

However it is not possible to make the best use of transparency of aglass substrate and color tone such as metal gloss of a metal substrateand thus there is a problem with property for exhibiting clear surfacepattern of a substrate since in the method using an adhesive like themethod (1), no transparent adhesive having heat resistance and highadhesive property is available and also since in the method for makingthe substrate surface rough like the method (2), the substrate surfaceis made rough significantly. Further even if a transparent adhesive isdeveloped, since a fluorine-containing polymer composing a coating filmon a heating surface of cooking appliances, etc. is soft, the coatingfilm on the heating surface is injured, for example, due to a long termuse or by cleaning with a spatula or brush, and thus loweringtransparency and making surface pattern of a substrate unclear. Also forexample, due to abrasion of a windshield by a wiper, etc., inherentnon-sticking property and water-repellency of a fluorine-containingpolymer are lowered.

To solve those problems, there have been made attempts to endow thecoating film comprising a fluorine-containing polymer with hardness byadding a glassy or aluminum-based inorganic filler. However there wereproblems that the coating film becomes fragile, transparency is lowered,surface pattern of a substrate becomes unclear and even water-repellencyitself is lowered.

To cope with these problems, the proposals mentioned above have beenmade (in JP-A-4-124047, JP-A-4-325446, JP-A-5-24885, JP-A-4-359086,JP-A-5-170486, JP-A-5-213633, JP-A-5-51238, JP-A-6-329442,JP-A-6-340451, JP-A-7- 102207, JP-A-7-157335).

However as mentioned above, even by these conventional sol-gel methods,water-repellent coating films having excellent non-sticking property,abrasion resistance, heat resistance, oil-repellency and scratchresistance have not been obtained.

The water-repellent composite material obtained by applying the coatingcomposition of the present invention to the substrate can be used onvarious articles, equipment, appliances, building materials, etc.firstly because excellent water-repellency can be maintained for a longperiod of time, secondly because fine particles of thefluorine-containing ethylenic polymer (A) having functional group aredispersed uniformly in the coating film comprising the metal oxide (B)because of their good interfacial adhesion and the coating film hasenough hardness, transparency and adhesive property, and thirdly becausethe coating film comprising the fluorine-containing ethylenic polymer(A) having functional group and the metal oxide (B) has good heatresistance, abrasion resistance, scratch resistance, non-stickingproperty, water-repellency and anti-bacterial property.

The present invention can provide the water-repellent composite materialcomprising a substrate and, on a surface of the substrate, a coatingfilm which comprises the metal oxide (B) and fine particles of thefluorine-containing ethylenic polymer (A) having functional group andprepared by copolymerizing:

(a) 0.05 to 50% by mole of at least one of fluorine-containing ethylenicmonomers having at least one functional group selected from the groupconsisting of hydroxyl, carboxyl, a carboxylic salt group, a carboxylicester group and epoxy, and

(b) 50 to 99.95% by mole of a fluorine-containing ethylenic monomerhaving no functional group mentioned above; the fine particles of thepolymer (A) is dispersed in the metal oxide (B) layer.

Also the present invention can provide the water-repellent, compositematerial, in which the above-mentioned fluorine-containing ethylenicmonomer (a) having functional group is at least one offluorine-containing ethylenic monomers having functional group andrepresented by the formula (1):

CX₂═CX¹—R_(f)—Y  (1)

wherein Y is —CH₂OH, —COOH, a carboxylic salt group, a carboxylic estergroup or epoxy, X and X¹ are the same or different and each is hydrogenatom or fluorine atom, R_(f) is a divalent fluorine-containing alkylenegroup having 1 to 40 carbon atoms, a fluorine-containing oxyalkylenegroup having 1 to 40 carbon atoms, a fluorine-containing alkylene grouphaving ether group and 1 to 40 carbon atoms or a fluorine-containingoxyalkylene group having ether bond and 1 to 40 carbon atoms.

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned fluorine-containing polymer (A)having functional group is the polymer (I).

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned fluorine-containing polymer (A)having functional group is the polymer (II).

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned fluorine-containing polymer (A)having functional group is the polymer (III).

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned metal oxide (B) is a siliconoxide.

Also the present invention can provide the water-repellent. compositematerial, in which the above-mentioned metal oxide (B) is an aluminumoxide.

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned metal oxide (B) is a titaniumoxide.

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned substrate is a metallicsubstrate.

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned substrate is a non-metallicinorganic substrate.

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned substrate is a glass substrate.

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned substrate is a concretesubstrate.

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned substrate is a cement substrate.

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned substrate is a tile substrate.

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned substrate is a ceramic substrate.

Also the present invention can provide the water-repellent compositematerial, in which the above-mentioned substrate is a synthetic resinsubstrate.

Also the present invention can provide glass for cars produced by usingthe water-repellent composite material.

In principle the above-mentioned descriptions regarding the coatingcomposition, coating film and methods for production thereof are appliedto the water-repellent composite material of the present invention.Explained below are particularly preferable embodiments thereof.

Examples of the substrate usually used for the water-repellent compositematerial of the present invention are metallic plates of aluminum,stainless steel, iron and titanium; metallic plates subjected to hot-dipzinc coating, aluminum plating, etc.; metallic plates subjected tochemical conversion treatment such as oxidation with chromic acid,phosphoric acid, etc.; alumite-treated metallic plates subjected toanodizing; and the like.

Examples of the non-metallic inorganic substrate used usually are glasssubstrates such as crystallized glass, foam glass, heat reflectingglass, heat absorbing glass and multi-layered glass; ceramic substratessuch as tile, large size pottery plate, ceramic panel and brick; naturalstones such as granite and marble; concrete substrates such as highstrength concrete, glass fiber-reinforced concrete (GRC), carbonfiber-reinforced concrete (CFRC), lightweight aerated concrete (ALC) andcomposite ALC; cement substrates such as extrusion molded cement andcomposite molded cement; asbestos slate; enamelled steel plate; and thelike.

Further examples of the synthetic resin substrate used arepolycarbonate, polyester resin, acrylic resin, vinyl chloride resin,artificial marble (mainly comprising unsaturated polyester resin oracrylic resin), steel plates coated with vinyl chloride resin, acrylicresin or urethane resin, and the like.

Among them, where transparency is required, the non-metallic inorganicsubstrate of glass and the synthetic resin substrates of acrylic resinand polycarbonate, etc. are usually used.

A thickness of the metal oxide coating film of the above-mentionedwater-repellent composite material varies depending on kind and portionof appliances and utensils to which the film is applied. The thicknessis from 0.01 to 100 μm, preferably from 0.01 to 50 μm, particularlypreferably from 0.02 to 20 μm.

Appliances, utensils, building materials and portions thereof where thewater-repellent composite material of the present invention can be usedsuitably are raised and classified below by the fields applied, but arenot limited to them.

[1] Cooking apparatuses and utensils (including tablewares)

Cooking apparatuses and utensils require particularly water-repellency.Raised below are non-restricted typical examples thereof.

{circle around (1+L )} Pot

(a) Inner surface, inner lid, etc. of electric pots including electricwater heater

In these applications, water-repellency, non-sticking property(stain-proofing property for fur), hot water resistance andanti-bacterial property of the water-repellent composite material of thepresent invention can be used particularly effectively.

(b) Inner surface of inner pot, inner lid, etc. of gas and electric ricecooker and rice cooker with rice washing mechanism, etc.

In these applications, water-repellency, non-sticking property (for riceand scorching), stain-proofing property and heat resistance of thewater-repellent composite material of the present invention can be usedparticularly effectively. Further it is possible to inhibit lowering ofthe characteristics due to abrasion, scratch, etc. of the coating filmwhen cleaning with brush, etc.

{circle around (2+L )} Cooking apparatuses

(a) Surfaces of frying pan, vat, household hand mixer for cooking,crate, kitchen knife, molder for bread, reverse sheet for bread, doughdividing and rounding machine for making bread, etc., inner surfaces ofmixing bowl, rice chest, etc. and blade of the above-mentioned mixer

In these applications, water-repellency, non-sticking property(scorching and cohering stains), stain-proofing property and heatresistance of the water-repellent composite material of the presentinvention can be used particularly effectively. Further it is possibleto inhibit lowering of the characteristics due to abrasion, scratch,etc. of the coating film by metal spatula, etc.

(b) Inner surface, blade, etc. of electric food processors such aselectric food crusher for domestic use, electric food crusher, electricmeat grinder for kitchen use, electric blender for kitchen use andelectric mixer for kitchen use

In these applications, water-repellency, non-sticking property (forvegetable and meat juice) and stain-proofing property of thewater-repellent composite material of the present invention can be usedparticularly effectively.

{circle around (3+L )} Gas ovens with grill

(a) Top plate, side plate and surface of gas heaters such as gascontainer built-in type gas oven, surface of drip pan cover thereof,etc.

In these applications, water-repellency, non-sticking property (for oilstains), heat resistance and transparency (property for exhibiting clearsurface color and pattern) of the water-repellent composite material ofthe present invention can be used particularly effectively. Further itis possible to inhibit lowering of the characteristics due to abrasion,scratch, etc. of the coating film by cleaning with brush, etc.

{circle around (4+L )} Ranges with oven including toaster, range, etc.

(a) Inner surfaces (metallic portion) of ovens (range for kitchen use)such as oven for shop use, electric oven (including oven for shop use),electric oven with heating cabinet for shop use, cooking oven for shopuse and cooking range for shop use; ovens for making bread such asbaking oven for shop use and automatic baking appliance for domesticuse; electric oven and toaster such as toaster and toaster for bread;microwave range such as microwave range for shop use and microwave rangewith oven; and pans for ranges

In these applications, water-repellency, non-sticking property (for oiland scorching), stain-proofing property and heat resistance of thewater-repellent composite material of the present invention can be usedparticularly effectively. Further it is possible to inhibit abrasion andscratch of the coating film by spatula, brush, etc.

(b) Inner surface of doors of ranges with oven raised in above (a)

In these applications, water-repellency, non-sticking property, heatresistance and transparency of the water-repellent composite material ofthe present invention can be used particularly effectively. In case of amicrowave range, energy ray resistance can be used particularlyeffectively.

{circle around (5+L )} Pots and pans

(a) Inner surface of pots and pans such as glass pot, enamel pot,aluminum pot, electric frying pot, electric Tempura pot, electricpressure pot and electric pressure pot for stew, etc.

In these applications, water-repellency, non-sticking property (forscorching, cohering stains and oil in case of the frying pot and Tempurapot) and heat resistance of the water-repellent composite material ofthe present invention can be used particularly effectively. Further itis possible to inhibit abrasion and scratch of the coating film byspatula, brush, etc.

(b) Lids of pots and pans raised in above (a)

In these applications, not only the characteristics in above (a) butalso transparency of the water-repellent composite material of thepresent invention can be used particularly effectively.

{circle around (6+L )} Garbage disposer

Inner surface, etc. of garbage treating machines such as garbagedisposer for domestic use and garbage (waste) disposer for makingcompost

In these applications, water-repellency, non-sticking property andstain-proofing property of the water-repellent composite material of thepresent invention can be used particularly effectively.

{circle around (7+L )} Other heating apparatuses for cooking

(a) Heating surface, lid, etc. of griddle

In these applications, water-repellency, non-sticking property (forscorching and cohering stains) and heat resistance of thewater-repellent composite material of the present invention andtransparency in case of the lid can be used particularly effectively.Further it is possible to inhibit lowering of the characteristics andappearance due to abrasion and scratch of the coating film by metalspatula, etc.

(b) Cooking surface, etc. of electromagnetic cooking apparatuses such aselectromagnetic range and oven

In these applications, water-repellency, non-sticking property, heatresistance and transparency of the water-repellent composite material ofthe present invention can be used particularly effectively, and it ispossible to inhibit abrasion and scratch of the coating film by brush,etc.

(c) Inner surface, door inside, lid, etc. of electric steamer such asfood steamer for shop use

In these applications, water-repellency, non-sticking property,stain-proofing property, heat resistance and steam resistance of thewater-repellent composite material of the present invention can be usedparticularly effectively, and it is possible to inhibit abrasion andscratch of the coating film by brush, etc.

(d) Inner surface, lid, etc. of noodle boiler for shop use

In these applications, water-repellency, non-sticking property,stain-proofing property, heat resistance and hot water resistance of thewater-repellent composite material of the present invention can be usedparticularly effectively, and it is possible to inhibit abrasion andscratch of the coating film by brush, etc.

(e) Inner surface, inner surface (metallic portion) and door innersurface of cooking roaster for shop use, pan for range, etc.

In these applications, water-repellency, non-sticking property (forscorching and cohering stains) and heat resistance of thewater-repellent composite material of the present invention can be usedparticularly effectively, and it is possible to inhibit abrasion andscratch of the coating film by brush, etc.

(f) Inner surface, etc. of tableware and can washer for shop use

In these applications, water-repellency, non-sticking property,stain-proofing property and hot water resistance of the water-repellentcomposite material of the present invention can be used particularlyeffectively.

(g) Inner surface, door inner surface, etc. of heating cabinet for shopuse

In these applications, water-repellency, non-sticking property,stain-proofing property, transparency and heat resistance of thewater-repellent composite material of the present invention can be usedparticularly effectively.

Further examples of cooking apparatuses other than those mentionedabove, to which the water-repellent composite material of the presentinvention can be preferably applied are as follows.

Examples of cooking apparatuses within the range of above {circle around(1+L )}

(b) are rice gruel cooker, rice warmer, etc.

Examples of cooking apparatuses within the range of above {circle around(2+L )} (a) are various cooking utensils (for slicing), cookingutensils, cooking appliance, cooking machine (for food, etc.), ironplate for cooking, cooking appliances and facilities, barbecue utensils,food processing machine (with press machine, etc.), chocolatemanufacturing machine and ancillary temperature adjusting equipmentthereof for starting material, etc.

Examples of cooking appliances within the range of above {circle around(2+L )}(b) are cooking appliance for mixing, vegetable slicer, foodslicer, peeler, machine for cutting into cubes, food cutter, meatchopper, meat slicer, meat tenderizer, cutter mixer, mixer, food mixer,blender, apple processor, continuous egg opening machine, soy bean curdcutter, food molder, bread crumb coating machine, vegetable washer, etc.

Examples of cooking apparatuses within the range of above {circle around(3+L )} are range, portable heater, electric range, gas range, gas ovenwith grill, electric oven with grill, etc.

Examples of cooking apparatuses within the range of above {circle around(4+L )} are gas salamander, electric salamander, convention oven, bakingoven for making bread, etc.

Examples of cooking apparatuses within the range of above {circle around(5+L )} are wok set for Chinese dishes, one-handed pot, double-handedpot, gas fryer, Tempura fryer, oil filter unit, buckwheat pot, rotarypot, etc.

Examples of cooking apparatuses within the range of above {circle around(7+L )} are fryer for dumpling stuffed with minced meat, electromagneticrange, gas steamer, electric steamer, etc.

[2] Building material

Building materials also require water-repellency. Mentioned below areexamples of building materials and effects exhibited in addition towater-repellency.

{circle around (1+L )} Building glass

Building glass, polished flat glass for building (window glass), windowof stained glass, windshield glass, light shielding ratio adjustableglass, etc.

In these applications, transparency, scatter preventing property,stain-proofing property and flame retardancy of the water-repellentcomposite material of the present invention can be exhibitedparticularly effectively.

{circle around (2+L )} Outer wall material, roofing material andinterior and exterior material (made of metal)

(a) Exterior metallic building material for wall, metallic buildingmaterial, interior and exterior metallic panel for building, metallicfence, metallic tile, metallic panel for building, etc.

(b) Metallic roofing material, solar system built-in roofing material,etc.

(c) Metallic door, metallic grating, metallic shutter, metallic fence,metallic porch (for building), etc.

(d) Metallic blind (for outdoor use), gutter, sash, rain door, etc.

(e) Metallic ceiling panel, metallic floor tile, metallic wall panelcoated with decorative vinyl chloride sheet, etc.

(f) Metallic parking facilities for cars, metallic object of art, etc.

In these applications, weather resistance, stain-proofing property andtransparency (property for exhibiting clear surface pattern) of thewater-repellent composite material of the present invention can be usedparticularly effectively.

{circle around (3+L )} Outer wall material, roofing material andinterior and exterior material (non-metallic inorganic material)

(a) Segmental concrete block or concrete block bonded with a tile orsliced natural stone, segmental concrete road pavement board or concreteroad pavement board having a surface of rubber material, concrete boardwhich may be reinforced with GRC (fiber-reinforced concrete) wallmaterial

(b) Extrusion-molded cement such as cement having tile-like surface

(c) Building stone such as artificial stone

(d) Building tile, luster-finished tile, floor tile, ceramic tile andborder tile made of pottery

(e) Exterior materials for building and for wall such as non-metallicexterior material for building, building material, building panel andwall tile for building

(f) Roofing material such as solar system built-in roofing material madeof ceramic

(g) Gravestone and grave-post

(h) Small sculpture, standing sculpture, image, bust and other object ofart made of stone, concrete or marble

In these applications, weather resistance, stain-proofing property,water-proof property, transparency (property for exhibiting clearsurface pattern), processability and adhesive property of thewater-repellent composite material of the present invention, abrasionresistance thereof in case of above (c) and weathering preventingproperty thereof in cases of (g) and (h) can be used particularlyeffectively.

{circle around (4+L )} Outer wall material, roofing material andinterior and exterior material (resinous)

(a) Floor panel, ceiling panel, etc.

(b) Grating, gutter, blind and door including those for indoor use, etc.

(c) Plastic panel for concrete

(d) Gasket for building

(e) Curtain, cover and sunshield with an insect-proofing, ultravioletray and heat shielding and scatter preventing film

(f) Flooring material made of stone or flooring material made ofpolyvinyl chloride and having a surface of stone pattern

(g) Solar system built-in plastic roofing material

(h) Sectional polyvinyl chloride tile having clearance and being capableof draining water

(i) Synthetic resin sash

(j) Decorative board for counter, furniture, sill, wall panel,bucksplash, baseboard, walls of bathroom and shower room, etc.

(k) Prefabricated assembly set for washstand, shower room, lavatory,transferable toilet, public toilet, etc.

(l) Prefabricated assembly set for sauna room, garage, etc.

In these applications, weather resistance, stain-proofing property,transparency (property for exhibiting clear surface pattern), waterresistance, processability and adhesive property of the water-repellentcomposite material of the present invention can be used particularlyeffectively.

{circle around (5+L )} Outer wall material and roofing material (made ofwood)

(a) Timber for household utensils, wooden board and decorative board forbuilding such as veneer and wooden panel, etc.

(b) Wooden fence, interior door and window frame, etc.

(c) Wooden panel for building produced by adhering elastic rubbermaterial on the back of plywood

(d) Wooden assembly set for building

In these applications, weather resistance, stain-proofing property,transparency (property for exhibiting clear surface pattern), waterresistance, processability and adhesive property of the water-repellentcomposite material of the present invention can be used particularlyeffectively.

{circle around (6+L )} Furniture

(a) Glass showcase, wagon, display wagon, display panel, display stand,meal conveying wagon, flower stand, etc.

(b) Shelf, screen, desk, sofa, shelf for chest of drawers, etc.

(c) Telephone booth made of metal or various materials

In these applications, stain-proofing property, transparency (propertyfor exhibiting clear surface pattern), water resistance andprocessability of the water-repellent composite material of the presentinvention and further property for preventing paper from being pasted,adhesive property and abrasion resistance thereof in case of above (c)can be used particularly effectively.

{circle around (7+L )} Apparatuses for household and shop uses

(a) Gas oven with grill, range hood, ventilation hood, etc.

(b) Metallic duct for central heating, ventilator, air conditioner, etc.

In these applications, stain-proofing property, processability andadhesive property of the water-repellent composite material of thepresent invention can be used particularly effectively.

{circle around (8+L )} Housing apparatuses and facilities

(a) Coordinated kitchen units including range for kitchen (oven), sink,etc.

(b) Electrically heated, gas heated and oil heated water heaters(including instantaneous water heater)

(c) Wall-mounted washbasin, washstand, hair washing appliance fordomestic use, washstand with hair washing function, washbasin forwashstand, washbasin with cover, bow window type washstand, etc.

(d) Flush toilet stool, small size chamber pot for car, urinal, toiletstool with urinalyzer, toilet stool for little children, toilet stoolwith hot water washing function, toilet seat with deodorizing unit andwater tank for flush toilet

In these applications, stain-proofing property, property for exhibitingclear surface pattern (transparency), processability, abrasionresistance and anti-bacterial property of the water-repellent compositematerial of the present invention can be used particularly effectively.

(e) Lining for bathrooms including shower room, sauna bath for domesticand shop uses, bath tubs such as prefabricated bath tub and bath tubwith bubble generator and bath utensils such as handle mounted on bathtub and soap holder

(f) Escalator, elevator (including those for private houses), etc.

In these applications, stain-proofing property, property for exhibitingclear surface pattern (transparency) and processability of thewater-repellent composite material of the present invention and furtherheat resistance thereof in case of above (a), (b) and (e), abrasionresistance thereof in case of above (c) to (e) and sliding property andcorrosion resistance thereof in case of above (f) can be usedparticularly effectively.

{circle around (9+L )} Construction

(a) Sign for bus stop, sign for street, sign mounted on guardrail, etc.

(b) Signals such as luminous signal and mechanical signal

(c) Guardrail produced by using various materials

(d) Utility pole produced by using various materials

(e) Sound-proof wall

(f) Plastic molding panel for concrete for building and construction

In these applications, weather resistance, stain-proofing property,transparency, processability and adhesive property of thewater-repellent composite material of the present invention and furthermold-release property thereof in case of above (f) can be usedparticularly effectively.

[3] Cars

There are many parts of car which require water-repellency against rainwater and water used for washing. Exemplified below are parts for carwhich require water-repellency, and other characteristics to beexhibited in addition to water repellency are also referred to. Thepresent invention also relates to these parts and cars.

{circle around (1+L )}Glass for car

Application: Windshield glass, window glass, glass for sunroof, glasswith heating coil, etc.

Substrate: Glass and polycarbonate

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

In these applications, transparency, stain-proofing property, resistanceto abrasion and scratch by a wiper, etc. and weather resistance of thewater-repellent composite material of the present invention can be usedparticularly effectively.

{circle around (2+L )} Mirror for car

Application: Rearview mirror, room mirror, door mirror, etc.

Substrate: Mirror and glass

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

In these applications, transparency, stain-proofing property, scratchresistance, etc. of the water-repellent composite material of thepresent invention can be used particularly effectively.

{circle around (3+L )} Car body

Application: Side body, hood, roof plate, fender, spoiler, bumper, etc.

Substrate: Steel sheet, surfaces coated with acrylic resin, etc.,polypropylene (PP), urethane, and polyester

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

In these applications, transparency, stain-proofing property, abrasionresistance, scratch resistance, etc. of the water-repellent compositematerial of the present invention can be used particularly effectively.

{circle around (4+L )} Light and cover for light

Application: Cover, lamp, etc. for headlight, turn signal, brake light,taillight, fog lamp and backup light

Substrate: Glass and polycarbonate

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

In these applications, transparency, stain-proofing property, scratchresistance, etc. of the water-repellent composite material of thepresent invention can be used particularly effectively.

[4] Others

{circle around (1+L )} Glass for train

Application: Outer surface of window glass

Substrate: Glass

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

In these applications, transparency, stain-proofing property, etc. ofthe water-repellent composite material of the present invention can beused particularly effectively.

{circle around (2+L )} Insulator and pantograph

Application: Surface

Substrate: Pottery

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

In these applications, water repellency, stain-proofing property,scratch resistance, insulating property, etc. of the water-repellentcomposite material of the present invention can be used particularlyeffectively.

{circle around (3+L )} Bulb, bulb cover material (particularly forexterior use)

Application: Bulb surface, cover surface and shade surface

Substrate: Glass, PP and polycarbonate

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

In these applications, water-repellency, stain-proofing property,scratch resistance, insulating property, etc. of the water-repellentcomposite material of the present invention can be used particularlyeffectively.

Among the water-repellent composite materials, by applying the coatingcomposition particularly to glass, a water-repellent glass having highhardness and transparency can be obtained. Water-repellent glass whichis produced by applying, to glass, the water-repellent coatingcomposition of the present invention comprising the water-repellent fineparticles of the fluorine-containing polymer (A) having functional groupand the metal oxide (B) and has a coating film containing the dispersedwater-repellent fine particles therein, is excellent particularly intransparency and abrasion resistance. For example, when thewater-repellent glass is used as a windshield glass for car, itswater-repellency is hardly lowered even due to abrasion by a wiper.

In the water-repellent coating composition used for producingwater-repellent glass of the present invention, for example, it ispreferable that the fluorine-containing polymer (A) comprises theabove-mentioned water-repellent fine particles having water repellency,namely fine particles selected from above (I), (II) and (III), that themetal oxide (B) comprises mainly a silica sol prepared by hydrolyzingand poly-condensating a silane compound such as alkoxysilane and as thecase demands, contains an oxide of Al, Zr, Ti, or the like and that thesolvent (C) is selected from alcohols and water.

The water-repellent glass of the present invention can be produced bypreparing, by the above-mentioned preparation process, the compositioncomprising mainly water-repellent fine particles of thefluorine-containing polymer (A) having functional group and the silicasol, applying the composition to the glass and then baking the coatedglass.

Glass used as a substrate can be selected from silicate glass such assilica glass, alkaline silicate glass, alkaline lead glass, soda-limeglass, potash lime glass or barium glass, boro-silicate glass containingB₂O₃ and SiO₂, phosphate glass containing P₂O₅, etc.

Also the glass used may be colored glass, tempered glass, laminatedglass or glass for mirror. Though enough adhesion of the water-repellentcoating film even to the smooth surface of glass is obtained, in orderto enhance adhesion of the water-repellent coating film, it is possibleto carry out hydrofluoric acid treatment or plasma etching so as to makethe glass surface finely rough.

The water-repellent coating film of water-repellent glass of the presentinvention is, for example, a coating film which comprises thewater-repellent fine particles of the fluorine-containing polymer (A)having functional group and silica (SiO₂) and contains thewater-repellent fine particles of the fluorine-containing polymer (A)having functional group in dispersed state.

Based on the whole coating film, a content of the fluorine-containingpolymer (A) having functional group in the water-repellent coating filmis from 5 to 85% by weight, preferably from 10 to 80% by weight and acontent of silica is from 15 to 95% by weight, preferably from 20 to 90%by weight.

A thickness of the above-mentioned water-repellent coating film variesdepending on purposes and applications and is from 0.01 to 2 μm,preferably from 0.02 to 1 μm, particularly preferably from 0.1 to 1 μm.

EMBODIMENT 2 (stain-proofing composite material)

Lowering of original functions and appearances occurs in buildingmaterials, for example, exterior materials such as outer wall and roof,interior materials such as inner wall, ceiling and floor, etc. due toadhesion of dust, smoke and soot thereon; in cooking appliances forprocessing and heating of foods or tablewares due to adhesion of edibleoil thereon; in office apparatuses using toner and represented by anelectrostatic process copying machine due to adhesion of toner andfingerprint thereon; and further in domestic electric appliances such asventilation fan due to adhesion of dust, nicotine and oil thereon.Therefore it is required that stain-proofing material is applied tothese portions where the mentioned adhesion possibly occurs.

In order to comply with such requirement, for example, with respect tobuilding materials such as building glass, various inner and exteriorwall materials, roofing materials and interior and outer materials andconstruction-related materials such as sign, signal, guardrail, utilitypole and sound-proof wall, since they are used exposed to environment,the surfaces thereof are required to have weather resistance,stain-proofing property against dust, exhaust gas and rain water,transparency and property for exhibiting clear surface pattern. Alsovarious furnitures, kitchen apparatuses such as gas oven with grill andrange hood, and housing facilities such as coordinated kitchen units,washstand, lavatory and bath room are required to have heat resistance,and non-sticking property and stain-proofing property against oil,scorch and fur. In Embodiment 2, all the mentioned products are referredto as “building material”. The substrates of these building materialsare made of glass, metal, ceramic, synthetic resin, concrete, or thelike. Some of them are not subjected to any treatment on their surfaces,but to cope with the mentioned requirement, to composite materials usedfor these building materials is applied a fluorine-containing polymerhaving excellent heat resistance, chemical resistance, corrosionresistance, weather resistance, surface characteristics (non-stickingproperty, low friction property, etc.), electric insulating property,etc. However since the fluorine-containing polymer has not enoughadhesion to a surface of substrate such as metal due to its excellentnon-sticking property, it is necessary to (1) use an adhesive or (2)carry out, on a surface of a substrate, sand blasting or etching byelectrochemical method to make the surface rough for adhering by ananchor.

However it is not possible to make the best use of transparency of aglass substrate and color tone such as metal gloss of a metal substrateand thus there is a problem with property for exhibiting clear surfacepattern, since in the method of using an adhesive in above (1), notransparent adhesive having heat resistance and high adhesive propertyis available and also since in the method of roughening the surface ofsubstrate in above (2), the surface is significantly roughened. Furthereven if a transparent adhesive is developed, since a fluorine-containingpolymer composing the coating film on the surface of the buildingmaterial is in general soft, the surface of the coating film is injured,for example, during a long term use or by cleaning with a brush, etc. tolower transparency and property for exhibiting clear surface pattern andalso inherent weather resistance, stain-proofing property,water-repellency and non-sticking property of the fluorine-containingpolymer are lowered due to abrasion of the film. Further since thepolymer is soft, when the coating film is applied to an exteriorbuilding material, foreign matters, dusts and stains easily enter thecoating film and therefore there is a case where stains are difficult tobe removed.

To solve that, an attempt to endow the coating film comprising thefluorine-containing polymer with hardness by adding a glassy oraluminum-based inorganic filler has been made, but there was a problemthat the coating film becomes fragile and transparency and property forexhibiting clear surface pattern are lowered.

Also various studies for giving water-repellency to glass have been madefor the purpose to repel rain water on a window glass or fender mirrorof car in rainy days and make field of view good. It is considered thatthe results of such studies are used in the fields requiringstain-proofing property.

In this regard, there are proposals as cited above (JP-A-4-124047,JP-A-4-325446, JP-A-5-24885, JP-A-4-359086, JP-A-5-170486,JP-A-5-213633, JP-A-5-51238, JP-A-6-329442, JP-A-6-340451,JP-A-7-102207, and JP-A-7-157335).

However as mentioned above, even by these conventional sol-gel methods,a stain-proofing coating film having excellent transparency, abrasionresistance, heat resistance, oil- and water-repellency and scratchresistance has not been obtained.

The stain-proofing composite material obtained by applying the coatingcomposition of the present invention to a substrate can be used forvarious apparatuses, utensils and building materials firstly becauseexcellent stain-proofing property can be maintained for a long period oftime, secondly because the fine particles of the fluorine-containingethylenic polymer (A) having functional group are uniformly dispersed inthe coating film comprising the metal oxide (B) due to their goodinterfacial adhesion and the coating film has enough hardness,transparency and adhesive property, and thirdly because the coating filmcomprising the fluorine-containing ethylenic polymer (A) havingfunctional group and metal oxide (B) has good heat resistance, weatherresistance, abrasion resistance, scratch resistance, non-stickingproperty, water-repellency, anti-bacterial property, etc.

The present invention can provide the stain-proofing composite materialcomprising a substrate and, on a surface of the substrate, a coatingfilm which comprises the metal oxide (B) and fine particles of thefluorine-containing ethylenic polymer (A) having functional groupprepared by copolymerizing

(a) 0.05 to 50% by mole of at least one of fluorine-containing ethylenicmonomers having at least one functional group selected from hydroxyl,carboxyl, a carboxylic salt group, a carboxylic ester group and epoxyand

(b) 50 to 99.95% by mole of at least one of fluorine-containingethylenic monomers having no functional group mentioned above; the fineparticles of the polymer (A) are dispersed in the metal oxide (B) layer.

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the fluorine-containingethylenic monomer (a) having functional group is at least one offluorine-containing ethylenic monomers having functional group andrepresented by the formula (1):

CX₂═CX¹—R_(f)—Y  (1)

wherein Y is —CH₂OH, —COOH, a carboxylic salt group, a carboxylic estergroup or epoxy, X and X¹ are the same or different and each is hydrogenatom or fluorine atom, R_(f) is a divalent fluorine-containing alkylenegroup having 1 to 40 carbon atoms, a fluorine-containing oxyalkylenegroup having 1 to 40 carbon atoms, a fluorine-containing alkylene grouphaving ether group and 1 to 40 carbon atoms or a fluorine-containingoxyalkylene group having ether bond and 1 to 40 carbon atoms.

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the fluorine-containingethylenic polymer (A) having functional group is the above-mentionedpolymer (I).

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the fluorine-containingethylenic polymer (A) having functional group is the above-mentionedpolymer (II).

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the fluorine-containingethylenic polymer (A) having functional group is the above-mentionedpolymer (III).

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the metal oxide (B) is asilicon oxide.

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the metal oxide (B) is analuminum oxide.

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the metal oxide (B) is atitanium oxide.

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the substrate is a metallicsubstrate.

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the substrate is anon-metallic inorganic substrate.

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the non-metallic inorganicsubstrate is a glass, concrete, cement, tile or pottery substrate.

Also the present invention can provide the above-mentionedstain-proofing composite material, in which the substrate is a syntheticresin substrate.

In principle the above-mentioned descriptions regarding the coatingcomposition, coating film and methods for production thereof are appliedto the stain-proofing composite material of the present invention.Explained below are particularly preferable embodiments thereof.

Examples of the substrate used usually for the stain-proofing compositematerial of the present invention are metallic plates of aluminum,stainless steel, iron and titanium; metallic plates subjected to hot-dipzinc plating, aluminum plating, etc.; metallic plates subjected tochemical conversion treatment such as oxidation with chromic acid,phosphoric acid, etc.; alumite-treated metallic plates subjected toanodizing; and the like.

Examples of the non-metallic inorganic substrate used usually are glasssubstrates such as crystallized glass, foamed glass, heat reflectingglass, heat absorbing glass and multi-layered glass; ceramic substratessuch as tile, large size pottery plate, ceramic panel and brick; naturalstones such as granite and marble; concrete substrates such as highstrength concrete, glass fiber-reinforced concrete (GRC), carbonfiber-reinforced concrete (CFRC), lightweight aerated concrete (ALC) andcomposite ALC; cement substrates such as extrusion molded cement andcomposite molded cement; asbestos cement; enamelled steel plate; and thelike.

Further examples of the synthetic resin substrate used arepolycarbonate, polyester resin, acrylic resin, vinyl chloride resin,artificial marble (mainly comprising unsaturated polyester resin oracrylic resin), steel plates coated with vinyl chloride resin, acrylicresin or urethane resin, and the like.

Among them, where transparency is required, the non-metallic inorganicsubstrate of glass and the synthetic resin substrate of acrylic resinand polycarbonate are usually used.

A thickness of the metal oxide coating film of the above-mentionedstain-proofing composite material of the present invention variesdepending on kind and portion of appliances and utensils to which thefilm is applied. The thickness is from 0.01 to 100 μm, preferably from0.01 to 70 μm, particularly preferably from 0.02 to 50 μm.

Appliances, utensils, building materials and portions thereof where thestain-proofing composite material of the present invention can be usedsuitably are raised and classified below by the fields applied, but arenot limited to them.

[1] Cooking apparatuses and utensils (including tablewares)

Cooking apparatuses and utensils require particularly stain-proofingproperty because in many cases sticky oil and foods are used. Raisedbelow are non-restricted typical examples thereof.

{circle around (1+L )} Pot

(a) Inner surface, inner lid, etc. of electric pots including electricwater heater

In these applications, stain-proofing property (for fur), hot waterresistance and anti-bacterial property of the stain-proofing compositematerial of the present invention can be used particularly effectively.

(b) Inner surface of inner pot, inner lid, etc. of gas and electric ricecookers and rice cooker with rice washing mechanism, etc.

In these applications, stain-proofing property (for rice and scorching)and heat resistance of the stain-proofing composite material of thepresent invention can be used particularly effectively. Further it ispossible to inhibit lowering of the characteristics due to abrasion,scratch, etc. of the coating film by cleaning with brush, etc.

{circle around (2+L )} Cooking apparatuses

(a) Surfaces of frying pan, vat, household hand mixer for cooking,crate, kitchen knife, molder for bread, reverse sheet for bread, doughdividing and rounding machine for making bread, etc., inner surface ofmixing bowl, rice chest, etc. and blade of the above-mentioned mixer

In these applications, stain-proofing property (scorching and coheringstains) and heat resistance of the stain-proofing composite material ofthe present invention can be used particularly effectively. Further itis possible to inhibit lowering of the characteristics due to abrasion,scratch, etc. of the coating film by metal spatula, etc.

(b) Inner surface, blade, etc. of electric food processors such aselectric food crusher for domestic use, electric food crusher, electricmeat grinder for kitchen use, electric blender for kitchen use andelectric mixer for kitchen use

In these applications, stain-proofing property (for vegetable and meatjuice) of the stain-proofing composite material of the present inventioncan be used particularly effectively.

{circle around (3+L )} Gas oven with grill

(a) Surfaces of top plate, side plate and surface of gas ovens such asgas container built-in type oven, and drip pan cover thereof, etc.

In these applications, stain-proofing property (for oil stains), heatresistance and transparency (property for exhibiting clear color andpattern) of the stain-proofing composite material of the presentinvention can be used particularly effectively. Further it is possibleto inhibit lowering of the characteristics due to abrasion, scratch,etc. of the coating film by cleaning with brush, etc.

{circle around (4+L )} Ranges with oven including toaster, range, etc.

(a) Inner surfaces (metallic portion) of ovens (range for kitchen use)such as oven for shop use, electric oven (including oven for shop use),electric oven with heating cabinet for shop use, cooking oven for shopuse and cooking range for shop use; ovens for making bread such asbaking oven for shop use and automatic baking apparatus for domesticuse; electric oven and toaster such as toaster and toaster for bread;and microwave range such as microwave range for shop use and microwaverange with oven; pans for ranges; and the like.

In these applications, stain-proofing property (for oil and scorching)and heat resistance of the stain-proofing composite material of thepresent invention can be used particularly effectively. Further it ispossible to inhibit abrasion and scratch of the coating film by spatula,brush, etc.

(b) Inner surface of door of ranges with oven raised in above (a)

In these applications, stain-proofing property, heat resistance andtransparency of the stain-proofing composite material of the presentinvention can be used particularly effectively. In case of microwaverange, energy ray resistance can be used particularly effectively.

{circle around (5+L )} Pots and pans

(a) Inner surface of pots and pans such as glass pot, enamel pot,aluminum pot, electric frying pot, electric Tempura pot, electricpressure pot and electric pressure pot for stew, etc.

In these applications, stain-proofing property (for scorching, coheringstains and oil in case of the frying pot and Tempura pot) and heatresistance of the stain-proofing composite material of the presentinvention can be used particularly effectively. Further it is possibleto inhibit abrasion and scratch of the coating film by spatula, brush,etc.

(b) Lids of pots and pans raised in above (a)

In these applications, not only the characteristics in above (a) butalso transparency of the stain-proofing composite material of thepresent invention can be used particularly effectively.

{circle around (6+L )} Garbage disposer

Inner surface, etc. of garbage treating machines such as garbagedisposer for domestic use and garbage (waste) disposer for makingcompost

In these applications, stain-proofing property of the water-repellentcomposite material of the present invention can be used particularlyeffectively.

{circle around (7+L )} Other heating apparatuses for cooking

(a) Heating surface, lid, etc. of griddle

In these applications, stain-proofing property (for scorching andcohering stains) and heat resistance of the stain-proofing compositematerial of the present invention and transparency thereof in case ofthe lid can be used particularly effectively. Further it is possible toinhibit lowering of the characteristics and appearance due to abrasionand scratch of the coating film by metal spatula, etc.

(b) Cooking surface, etc. of electromagnetic cooking apparatuses such aselectromagnetic range and oven

In these applications, stain-proofing property, heat resistance andtransparency of the stain-proofing composite material of the presentinvention can be used particularly effectively, and it is possible toinhibit abrasion and scratch of the coating film by brush, etc.

(c) Inner surface, door inside, lid, etc. of electric steamer such asfood steamer for shop use

In these applications, stain-proofing property, heat resistance andsteam resistance of the stain-proofing composite material of the presentinvention can be used particularly effectively, and it is possible toinhibit abrasion and scratch of the coating film by brush, etc.

(d) Inner surface, lid, etc. of noodle boiler for shop use

In these applications, stain-proofing property, heat resistance and hotwater resistance of the stain-proofing composite material of the presentinvention can be used particularly effectively, and it is possible toinhibit abrasion and scratch of the coating film by brush, etc.

(e) Inner surface, inner surface (metallic portion) and door innersurface of cooking roaster for shop use, pan for range, etc.

In these applications, stain-proofing property (for scorching andcohering stains) and heat resistance of the stain-proofing compositematerial of the present invention can be used particularly effectively,and it is possible to inhibit abrasion and scratch of the coating filmby brush, etc.

(f) Inner surface, etc. of tableware and can washer for shop use

In these applications, stain-proofing property and hot water resistanceof the stain-proofing composite material of the present invention can beused particularly effectively.

(g) Inner surface, door inner surface, etc. of heating cabinet for shopuse

In these applications, stain-proofing property, transparency and heatresistance of the stain-proofing composite material of the presentinvention can be used particularly effectively.

Further as the cooking apparatuses other than those mentioned above, towhich the stain-proofing composite material of the present invention canbe used preferably, there can be raised the same ones as exemplified inthe above-mentioned Embodiment 1.

[2] Office automation-related apparatuses

In office automation-related apparatuses, in addition to parts wheretoner is used, there are many other portions which are apt to be easilydamaged by stain attributable to tobacco smoke, foreign matter,fingerprint, dust, etc. Mentioned below are non-restricted typicalexamples thereof.

(1) Electrophotographic copying machine, facsimile machine, wordprocessor, printer and other apparatuses with printing mechanism

The stain-proofing composite material is suitable as a material used forparts where toner is used or toner possibly adheres. Examples of suchparts are mentioned below.

{circle around (1+L )} Fixing roll

(a) For monochromatic printing

Substrate: Aluminum- or SUS-made substrate

When the stain-proofing composite material of the present inventioncomprising the above-mentioned substrate is used, a fixing roll havingexcellent stain-proofing property, durability and heat resistance can beobtained. Since the fluorine-containing polymer having functional groupitself has excellent adhesive property, no primer need be provided, andprocessability in production is excellent.

(b) For both monochromatic printing and color printing Substrate:Metallic substrate coated with silicon rubber or

urethane rubber and further with silicon oil for mold releasing

When the stain-proofing composite material of the present inventioncomprising the above-mentioned substrate is used, a fixing roll havingexcellent stain-proofing property, mold release property of paper andabrasion resistance can be obtained. Since the fluorine-containingpolymer having functional group itself has excellent adhesive property,no primer need be provided, and processability in production isexcellent.

{circle around (2+L )} Press roll (for both color and monochromaticprinting)

Substrate: Metallic substrate coated with silicon rubber or urethanerubber

When the stain-proofing composite material of the present inventioncomprising the above-mentioned substrate is used, a press roll havingexcellent stain-proofing property and abrasion resistance can beobtained. Since the fluorine-containing polymer having functional groupitself has excellent adhesive property, no primer need be provided, andprocessability in production is excellent because of excellent adhesiveproperty.

{circle around (3+L )} Charged roll (for both color and monochromaticprinting)

Substrate: Urethane rubber-made substrate

When the stain-proofing composite material of the present inventioncomprising the above-mentioned substrate is used, a charged roll havingexcellent stain-proofing property, mold release property of paper andabrasion resistance can be obtained. Since the fluorine-containingpolymer having functional group itself has excellent adhesive property,no primer need be provided, and processability in production isexcellent.

{circle around (4+L )} Transfer roll (for both color and monochromaticprinting)

Substrate: Urethane rubber-made substrate

When the stain-proofing composite material of the present inventioncomprising the above-mentioned substrate is used, a transfer roll havingexcellent stain-proofing property, mold release property of paper,abrasion resistance and elasticity can be obtained. Since thefluorine-containing polymer having functional group itself has excellentadhesive property, no primer need be provided, and processability inproduction is excellent.

{circle around (5+L )} Transfer belt (for both color and monochromaticprinting)

Substrate: Polyimide-made substrate

When the stain-proofing composite material of the present inventioncomprising the above-mentioned substrate is used, a transfer belt havingexcellent stain-proofing property and abrasion resistance can beobtained. Since the fluorine-containing polymer having functional groupitself has excellent adhesive property, no primer need be provided, andprocessability in production is excellent.

{circle around (6+L )} Separating claw and fixing bearing (surface)

Substrate: Heat resistant resin-made substrate (for example,polyphenylene sulfide (PPS), polyamideimide, polyether imide,polyoxymethylene (POM), polyether ether ketone (PEEK), or the like)

When the stain-proofing composite material of the present inventioncomprising the above-mentioned substrate is used, a separating clawhaving excellent stain-proofing property, abrasion resistance and paperfeed property and hardly injuring a roll and a fixing bearing having lowfriction property and excellent abrasion resistance and heat resistancecan be obtained. Since the fluorine-containing polymer having functionalgroup itself has excellent adhesive property, no primer need beprovided, and processability in production is excellent.

{circle around (7+L )} Paper delivery roll and paper delivery guide

Substrate: Resin-made substrate (for example, PPS, polyamideimide,polyether imide, POM, PEEK, or the like)

When the stain-proofing composite material of the present inventioncomprising the above-mentioned substrate is used, a paper delivery rolland paper delivery guide having excellent stain-proofing property andabrasion resistance can be obtained. Since the fluorine-containingpolymer having functional group itself has excellent adhesive property,no primer need be provided, and processability in production isexcellent.

Also the stain-proofing composite material of the present invention canbe used on the following parts for office automation-related apparatusesparticularly by making the use of its good transparency.

{circle around (8+L )} Cathode ray tube, liquid crystal panel and plasmadisplay (front surface)

Substrate: Glass

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

When this stain-proofing composite material is used, a cathode ray tube,liquid crystal panel and plasma display having excellent transparencyand stain-proofing property against dust, fingerprint, etc. can beobtained. No primer need be provided, and processability in productionis excellent.

{circle around (9+L )} Contact glass (surface)

Substrate: Glass

When the stain-proofing composite material of the present inventioncomprising the above-mentioned substrate is used, a contact glass havingexcellent transparency and stain-proofing property against dust,fingerprint, etc. and excellent stain-proofing property against inkeraser, marking ink, etc. can be obtained. Since the fluorine-containingpolymer having functional group itself has excellent adhesive property,no primer need be provided, and processability in production isexcellent.

[3] Building material

Some of building materials also require stain-proofing property.Mentioned below are examples of those building materials and effectsexhibited in addition to stain-proofing property.

{circle around (1+L )} Glass for building

Building glass, polished flat glass for building (window glass), windowof stained glass, windshield glass, light shielding ratio adjustableglass, etc.

In these applications, transparency, non-sticking property and flameretardancy of the stain-proofing composite material of the presentinvention can be used particularly effectively.

{circle around (2+L )} Outer wall material, roofing material andinterior and exterior material (made of metal)

(a) Exterior metallic building material for wall, metallic buildingmaterial, interior and exterior metallic panels for building, metallicfence, metallic tile, metallic building panel, etc.

(b) Metallic roofing material, solar system built-in roofing material,etc.

(c) Metallic door, metallic grating, metallic shutter, metallic fence,metallic porch (for building), etc.

(d) Metallic blind (for outdoor), gutter, sash, rain door, etc.

(e) Metallic ceiling panel, metallic floor tile, metallic wall panelcoated with vinyl chloride decorative sheet, etc.

(f) Metallic parking facilities for cars, metallic object of art, etc.

In these applications, weather resistance, non-sticking property andtransparency (property for exhibiting clear surface pattern) of thestain-proofing composite material of the present invention can be usedparticularly effectively.

{circle around (3+L )} Outer wall material, roofing material andinterior and exterior material (non-metallic inorganic material)

(a) Segmental concrete block or concrete block bonded with a tile orsliced natural stone, segmental concrete road pavement board or concreteroad pavement board having a surface of rubber material, concrete boardwhich may be reinforced with GRC (fiber-reinforced concrete) wallmaterial, etc.

(b) Extrusion-molded cement such as cement having tile-like surface

(c) Building stone such as artificial stone

(d) Tiles such as building tile, luster-finished tile, floor tile,ceramic tile and border tile made of pottery

(e) Exterior material for building and for wall such as non-metallicexterior material for building, building material, building panel andwall tile for building

(f) Roofing material such as solar system built-in roofing material madeof ceramic

(g) Gravestone and grave-post

(h) Small sculpture, standing sculpture, image, bust and other object ofart made of stone, concrete or marble

In these applications, weather resistance, non-sticking property,water-proof property, transparency (property for exhibiting clearsurface pattern), processability and adhesive property of thestain-proofing composite material of the present invention, abrasionresistance thereof in case of above (c) and weathering preventingproperty thereof in cases of (g) and (h) can be used particularlyeffectively.

{circle around (4+L )} Outer wall material, roofing material andinterior and exterior material (made of resin)

(a) Floor panel, ceiling panel, etc.

(b) Grating, gutter, blind and door including those for indoor use, etc.

(c) Plastic molding panel for concrete

(d) Gasket for building

(e) Curtain, cover, sunshield, etc. with an insect-proof, ultravioletray and heat shielding and scatter preventing film

(f) Flooring material made of stone or flooring material made ofpolyvinyl chloride and having a surface of stone pattern

(g) Solar system built-in plastic roofing material

(h) Sectional polyvinyl chloride tile having clearance and being capableof draining water

(i) Synthetic resin sash

(j) Decorative board for counter, furniture, sill, wall panel,bucksplash, baseboard, and walls of bathroom and shower room

(k) Prefabricated assembly set for washstand, shower room, lavatory,transferable toilet, public toilet, etc.

(l) Prefabricated assembly set for sauna room, garage, etc.

In these applications, weather resistance, non-sticking property,transparency (property for exhibiting clear surface pattern), waterresistance, processability and adhesive property of the stain-proofingcomposite material of the present invention can be used particularlyeffectively.

{circle around (5+L )} Outer wall material and roofing material (made ofwood)

(a) Timber for household utensils, wooden board and decorative board forbuilding such as plywood and wooden panel, etc.

(b) Wooden fence, interior door and window frame, etc.

(c) Wooden panel for building produced by adhering elastic rubbermaterial on the back of plywood

(d) Wooden assembly set for building

In these applications, weather resistance, non-sticking property,transparency (property for exhibiting clear surface pattern), waterresistance, processability and adhesive property of the stain-proofingcomposite material of the present invention can be used particularlyeffectively.

{circle around (6+L )} Furniture

(a) Glass showcase, wagon, display wagon, display panel, display stand,meal conveying wagon, flower stand, etc.

(b) Shelf, screen, desk, sofa, shelf for chest of drawers, etc.

(c) Telephone booth made of metal or various materials

In these applications, non-sticking property, transparency (property forexhibiting clear surface pattern), water resistance and processabilityof the stain-proofing composite material of the present invention andfurther property for preventing paper from being pasted, adhesiveproperty and abrasion resistance thereof in case of above (c) can beused particularly effectively.

{circle around (7+L )} Apparatuses for household and shop uses

(a) Gas oven with grill, range hood, ventilation hood, etc.

(b) Metallic duct for central heating, ventilator, air conditioner, etc.

In these applications, non-sticking property, processability andadhesive property of the stain-proofing composite material of thepresent invention can be used particularly effectively.

{circle around (8+L )} Housing apparatuses and facilities

(a) Coordinated kitchen units including kitchen range (oven), sink, etc.

(b) Electrically heated, gas heated and oil heated water heaters(including instantaneous water heater)

(c) Wall-mounted washbasin, washstand, hair washing appliance fordomestic use, washstand with hair washing function, washbasin forwashstand, washbasin with cover, bow window type washstand, etc.

(d) Flush toilet stool, small size chamber pot for car, urinal, toiletstool with urinalyzer, toilet stool for little children, toilet stoolwith hot water washing function, toilet seat with deodorizing unit andwater tank for flush toilet

In these applications, non-sticking property, property for exhibitingclear surface pattern (transparency), processability, abrasionresistance and anti-bacterial property of the stain-proofing compositematerial of the present invention can be used particularly effectively.

(e) Lining for bathrooms including shower room, sauna bath for domesticand shop uses, bath tubs such as prefabricated bath tub and bath tubwith bubble generator and bath utensils such as handle mounted on bathtub and soap holder

(f) Escalator, elevator (including those for private houses), etc.

In these applications, non-sticking property, property for exhibitingclear surface pattern (transparency) and processability of thestain-proofing composite material of the present invention, heatresistance thereof in cases of above (a), (b) and (e), abrasionresistance thereof in cases of above (c) to (e) and sliding property andcorrosion resistance thereof in case of above (f) can be usedparticularly effectively.

{circle around (9+L )} Construction

(a) Sign for bus stop, sign for street, sign mounted on guardrail, etc.

(b) Signals such as luminous signal and mechanical signal

(c) Guardrail produced by using various materials

(d) Utility pole produced by using various materials

(e) Sound-proof wall

(f) Plastic molding panel for concrete for building and construction,etc.

In these applications, weather resistance, non-sticking property,transparency, processability and adhesive property of the stain-proofingcomposite material of the present invention and further mold-releaseproperty thereof in case of above (f) can be used particularlyeffectively.

[4] Car-related articles (including motorbike)

Stains on exterior members of car such as body and window glass due toforeign matters in the air, mud, dusts, oil, etc. can be prevented. Alsowith respect to interior of car, there are the same effects as in theabove-mentioned housing facilities. In addition, the same effects areobtained with respect to parts such as wheel, mirror and light.

{circle around (1+L )} Body of car

Application: Surface of body, bumper, spoiler

Substrate: Acrylic resin-coated surface, steel sheet, PP, urethaneresin, polyester

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property against dusts and soots, transparency,property for exhibiting clear surface pattern and scratch resistance

{circle around (2+L )} Window of car

Application: Windshield glass, side window glass, rearview glass, windowglass for train

Substrate: Glass

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property against dusts, soots and finger-print,water-repellency, transparency, abrasion resistance for wiper

{circle around (3+L )} Light (headlight, taillight, turn signal, etc.)

Application: Cover surface and bulb surface

Substrate: Polycarbonate, glass

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property against dusts and soots,water-repellency, transparency, scratch resistance

{circle around (4+L )} Interior material of car

Application: Dashboard, front panel, rear panel, trunk room

Substrate: Urethane resin, PP

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proof property against nicotine, dusts and finger-print,transparency, property for exhibiting clear surface pattern

{circle around (5+L )} Mirrors

Application: Fender mirrors, rearview mirror

Substrate: Glass

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property against dusts and soots,water-repellency, transparency

{circle around (6+L )} Wheel

Application: Surface

Substrate: Aluminum, cast iron, PP, ABS, PA, PC, PPE, alloys

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property against dusts and mud, scratchresistance against stone, etc., transparency, property for exhibitingclear surface pattern

[5] Domestic electric appliances

The stain-proofing composite material of the present invention can beused on not only the above-mentioned electric apparatuses for kitchenuse but also parts of various electric appliances where stains become aproblem. Typical examples thereof are mentioned below.

{circle around (1+L )} Air conditioner (including cooling and heating)

Application: Louver of indoor unit, exterior of outdoor unit, aluminumfin, propeller

Substrate: PP, aluminum, galvanized steel sheet, galvanized steel plate

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property and removing property against dusts,soots and nicotine, transparency, property for exhibiting clear surfacepattern, processability

{circle around (2+L )} Ventilation fan

Application: Fan, frame, cover

Substrate: PP, aluminum, galvanized steel sheet, galvanized steel plate

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property against oil and cohering stain,transparency, property for exhibiting clear surface pattern, abrasionresistance and scratch resistance for use of brush, etc. for cleaning

{circle around (3+L )} Electric bulb (or shade thereof

Application: Surfaces of bulb, cover and shade

Substrate: Glass, PP

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property against dusts and soots, transparency,scratch resistance

{circle around (4+L )} Refrigerator

Application: Inside and outside surfaces

Substrate: PP, aluminum, SUS, galvanized steel sheet, galvanized steelplate

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property against food and seasoning, coheredstain removing property, transparency, property for exhibiting clearsurface pattern, processability

[6] Others

{circle around (1+L )} Insulator, pantograph

Application: Surface

Substrate: Ceramic

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property against dusts and soots, scratchresistance, processability

{circle around (2+L )} Bolt

Application: Surface

Substrate: Iron, SUS

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Stain-proofing property, rust-proof property, impact resistance,processability

EMBODIMENT 3 (Non-sticking composite material)

In cooking apparatuses for processing and heating foods and tablewares,office machines using toner such as an electrostatic process copyingmachine and domestic electric appliances such as a ventilation fan, whenfoods, toner, oil, etc. adhere to apparatuses, appliances and partsthereof, inherent functions and appearance thereof are lost. Thereforeit is required that a non-sticking material is applied to parts wheresuch adhesion possibly occurs.

As the non-sticking material, fluorine-containing materials,particularly fluorine-containing resins are generally known and actuallyused.

However the above-mentioned fluorine-containing resins have substantialproblem that they do not have enough adhesion to a substrate of metal,glass, etc. because of their excellent non-sticking property.

To satisfy such requirement, a fluorine-containing polymer havingexcellent heat resistance, chemical resistance, corrosion resistance,weather resistance, surface characteristics (non-sticking property, lowfriction property, etc.), electric insulating property, etc. is used fora composite material used, for example, for cooking apparatuses,particularly heating surfaces of rice cooker, electric griddle, etc.However the fluorine-containing polymer do not have enough adhesion to ametal surface due to its excellent non-sticking property, and thereforeit is necessary to (1) use an adhesive or (2) carry out sand blasting orelectrochemical etching on a substrate surface to make the surface roughfor adhering by anchor effect.

However it is not possible to make the best use of transparency of aglass substrate and color tone such as metal gloss of a metal substrateand thus there is a problem with property for exhibiting clear surfacepattern, since in the method of using an adhesive in above (1), notransparent adhesive having excellent heat resistance and high adhesiveproperty is available and since in the method of roughening the surfaceof substrate in above (2), the surface is significantly roughened.Further even if a transparent adhesive is developed, since afluorine-containing polymer contained in the coating film on the heatingsurface is in general soft, the surface of the coating film is injuredduring a long term use or by cleaning with a spatula, brush, etc. tolower transparency and property for exhibiting clear surface pattern andalso inherent non-sticking property and water-repellency of thefluorine-containing polymer are lowered due to abrasion of the film.

To solve that, an attempt to endow the coating film comprising thefluorine-containing polymer with hardness by adding an inorganic fillerof glass or aluminum has been made, but there was a problem that thecoating film became fragile, transparency was lowered and a surfacepattern of a substrate became unclear.

Also various studies for giving water-repellency to glass have been madefor the purpose to repel rain water on a window glass or fender mirrorof car in rainy days and make field of view good. It is considered thatthe results of such studies are used in the fields requiringnon-sticking property.

In this regard, there are proposals as cited above (JP-A-4-124047,JP-A-4-325446, JP-A-5-24885, JP-A-4-359086, JP-A-5-170486,JP-A-5-213633, JP-A-5-51238, JP-A-6-329442, JP-A-6-340451,JP-A-7-102207, and JP-A-7-157335).

However as mentioned above, even by those conventional sol-gel methods,a non-sticking coating film having excellent transparency, abrasionresistance, heat resistance, water- and oil-repellency and scratchresistance has not been obtained.

The non-sticking composite material obtained by applying the coatingcomposition of the present invention to a substrate can be used forvarious apparatuses, utensils and building materials firstly becauseexcellent non-sticking property can be maintained for a long period oftime, secondly because the fine particles of the fluorine-containingethylenic polymer (A) having functional group are uniformly dispersed ina coating film comprising the metal oxide (B) due to their goodinterfacial adhesion and the coating film has enough hardness,transparency and adhesive property, and thirdly because the coating filmcomprising the fluorine-containing ethylenic polymer (A) havingfunctional group and metal oxide (B) has good heat resistance, abrasionresistance, scratch resistance, stain-proofing property, waterrepellency, anti-bacterial property, etc.

The present invention can provide the non-sticking composite materialcomprising a substrate and, on a surface of the substrate, a coatingfilm which comprises the metal oxide (B) and fine particles of thefluorine-containing ethylenic polymer (A) having functional groupprepared by copolymerizing

(a) 0.05 to 50% by mole of at least one of fluorine-containing ethylenicmonomers having at least one functional group selected from hydroxyl,carboxyl, a carboxylic salt group, a carboxylic ester group and epoxyand

(b)50 to 99.95% by mole of at least one of fluorine-containing ethylenicmonomers having no functional group mentioned above; the fme particlesof the polymer (A) are contained in dispersed state in the metal oxide(B) layer.

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the fluorine-containing ethylenic monomer(a) having functional group is at least one of fluorine-containingethylenic monomers having functional group and represented by theformula (1):

CX₂═CX¹—R_(f)—Y  (1)

wherein Y is —CH₂OH, —COOH, a carboxylic salt group, a carboxylic estergroup or epoxy, X and X¹ are the same or different and each is hydrogenatom or fluorine atom, R_(f) is a divalent fluorine-containing alkylenegroup having 1 to 40 carbon atoms, a fluorine-containing oxyalkylenegroup having 1 to 40 carbon atoms, a fluorine-containing alkylene grouphaving ether group and 1 to 40 carbon atoms or a fluorine-containingoxyalkylene group having ether bond and 1 to 40 carbon atoms.

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the fluorine-containing ethylenic polymer(A) having functional group is the above-mentioned polymer (I).

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the fluorine-containing ethylenic polymer(A) having functional group is the above-mentioned polymer (II).

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the fluorine-containing ethylenic polymer(A) having functional group is the above-mentioned polymer (III).

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the metal oxide (B) is a silicon oxide.

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the metal oxide (B) is an aluminum oxide.

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the metal oxide (B) is a titanium oxide.

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the substrate is a metallic substrate.

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the substrate is a glass substrate.

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the substrate is a synthetic resinsubstrate.

Also the present invention can provide the above-mentioned non-stickingcomposite material, in which the substrate is a ceramic substrate.

In principle the above-mentioned descriptions regarding the coatingcomposition, coating film and methods for production thereof are appliedto the non-sticking composite material of the present invention.Explained below are particularly preferable embodiments thereof.

Examples of the substrate which can be used for the non-stickingcomposite material of the present invention are all the substratesmentioned above, and examples of the metallic substrate usedparticularly in many cases are, for instance,

{circle around (1+L )} Cold rolled steel sheet

{circle around (2+L )} Plated steel plates, for example, Zn-plated steelplate, Zn alloy-plated steel plate, Al-plated steel plate, Alalloy-plated steel plate, Cr-plated steel plate (TFS), Ni-plated steelplate, Cu-plated steel plate, galvanized steel plate, etc.

{circle around (3+L )} Aluminum plate

{circle around (4+L )} Titanium plate

{circle around (5+L )} Stainless steel plate, and the like.

In addition, where transparency is required, the ceramic substrate ofglass and the synthetic resin substrate of acrylic resin andpolycarbonate are usually used.

A thickness of the metal oxide coating film of the non-stickingcomposite material of the present invention varies depending on kind andportion of appliances and utensils to which the film is applied. Thethickness is from 0.01 to 100 μm, preferably from 0.01 to 50 μm,particularly preferably from 0.02 to 20 μm.

Apparatuses, utensils, building materials and portions thereof where thenon-sticking composite material of the present invention can be used areraised and classified below by the fields applied, but are not limitedto them.

[1] Cooking apparatuses and utensils (including tablewares)

Cooking apparatuses and utensils require particularly non-stickingproperty because sticky oil and foods are used in many cases. Raisedbelow are non-restricted typical examples thereof.

{circle around (1+L )} Pot

(a) Inner surface, inner lid, etc. of electric pots including electricwater steamer

In these applications, non-sticking property (stain-proofing propertyfor fur), hot water resistance and anti-bacterial property of thenon-sticking composite material of the present invention can be usedparticularly effectively.

(b) Inner surface of inner pot, inner lid, etc. of gas and electric ricecookers and rice cooker with rice washing mechanism, etc.

In these applications, non-sticking property (for rice and scorching),stain-proofing property and heat resistance of the non-stickingcomposite material of the present invention can be used particularlyeffectively. Further it is possible to inhibit lowering of thecharacteristics due to abrasion, scratch, etc. of the coating film bycleaning with brush, etc.

{circle around (2+L )} Cooking apparatuses p1 (a) Surfaces of fryingpan, vat, household hand mixer for cooking, crate, kitchen knife, molderfor bread, reverse sheet for bread, dough dividing and rounding machinefor making bread, etc., inner surface of mixing bowl, rice chest, etc.and blade of the above-mentioned mixer

In these applications, non-sticking property (scorching and coheringstains), stain-proofing property and heat resistance of the non-stickingcomposite material of the present invention can be used particularlyeffectively. Further it is possible to inhibit lowering of thecharacteristics due to abrasion, scratch, etc. of the coating film bymetal spatula, etc.

(b) Inner surface, blade, etc. of electric food processors such aselectric food crusher for domestic use, electric food crusher, electricmeat grinder for kitchen use, electric blender for kitchen use andelectric mixer for kitchen use

In these applications, non-sticking property (for vegetable and meatjuice) and stain-proofing property of the non-sticking compositematerial of the present invention can be used particularly effectively.

{circle around (3+L )} Gas oven with grill

(a) Top panel, side panel and surface of gas oven such as gas containerbuilt-in type oven, surface of drip pan cover thereof, etc.

In these applications, non-sticking property (for oil stains), heatresistance and transparency (property for exhibiting clear color andpattern) of the non-sticking composite material of the present inventioncan be used particularly effectively. Further it is possible to inhibitlowering of the characteristics due to abrasion, scratch, etc. of thecoating film by cleaning with brush, etc.

{circle around (4+L )} Range with oven including toaster, range, etc.

(a) Inner surfaces (metallic portion) of ovens such as oven for shopuse, electric oven (including oven for shop use), electric oven withheating cabinet for shop use, cooking oven for shop use and cookingrange for shop use; ovens for making bread such as baking oven for shopuse and automatic baking appliance for domestic use; electric oven andtoaster such as toaster and toaster for bread; microwave range such asmicrowave range for shop use and microwave range with oven; pans forranges; and the like.

In these applications, non-sticking property (for oil and scorching),stain-proofing property and heat resistance of the non-stickingcomposite material of the present invention can be used particularlyeffectively. Further it is possible to inhibit abrasion and scratch ofthe coating film by spatula, brush, etc.

(b) Inner surface of door of ranges with oven raised in above (a)

In these applications, non-sticking property, heat resistance andtransparency of the non-sticking composite material of the presentinvention can be used particularly effectively. In case of microwaverange, energy ray resistance can be used particularly effectively.

{circle around (5+L )} Pots and pans

(a) Inner surface of pots and pans such as glass pot, enamel pot,aluminum pot, electric frying pot, electric Tempura pot, electricpressure pot and electric pressure pot for stew, etc.

In these applications, non-sticking property (for scorching, coheringstains and oil in case of the frying pot and Tempura pot) and heatresistance of the non-sticking composite material of the presentinvention can be used particularly effectively. Further it is possibleto inhibit abrasion and scratch of the coating film by spatula, brush,etc.

(b) Lids of pots and pans raised in above (a)

In these applications, not only the characteristics in above (a) butalso transparency of the non-sticking composite material of the presentinvention can be used particularly effectively.

{circle around (6+L )} Garbage disposer

Inner surface, etc. of garbage treating machines such as garbagedisposer for domestic use and garbage (waste) disposer for makingcompost

In these applications, non-sticking property and stain-proofing propertyof the non-sticking composite material of the present invention can beused particularly effectively.

{circle around (7+L )} Other heating apparatuses for cooking

(a) Heating surface, cover, etc. of electric griddle

In these applications, non-sticking property (for scorching and coheringstains) and heat resistance of the non-sticking composite material ofthe present invention and transparency thereof in case of the cover canbe used particularly effectively. Further it is possible to inhibitlowering of the characteristics and appearance due to abrasion andscratch of the coating film by metal spatula, etc.

(b) Cooking surface, etc. of electromagnetic cooking apparatuses such aselectromagnetic range and oven

In these applications, non-sticking property, heat resistance andtransparency of the non-sticking composite material of the presentinvention can be used particularly effectively, and it is possible toinhibit abrasion and scratch of the coating film by brush, etc.

(c) Inner surface, door inner surface, cover, etc. of electric steamersuch as food steamer for shop use

In these applications, non-sticking property, stain-proofing property,heat resistance and steam resistance of the non-sticking compositematerial of the present invention can be used particularly effectively,and it is possible to inhibit abrasion and scratch of the coating filmby brush, etc.

(d) Inner surface, cover, etc. of noodle boiler for shop use

In these applications, non-sticking property, stain-proofing property,heat resistance and hot water resistance of the non-sticking compositematerial of the present invention can be used particularly effectively,and it is possible to inhibit abrasion and scratch of the coating filmby brush, etc.

(e) Inner surface, inner surface (metallic portion) and door innersurface of cooking roaster for shop use, pan for range, etc.

In these applications, non-sticking property (for scorching and coheringstains) and heat resistance of the non-sticking composite material ofthe present invention can be used particularly effectively, and it ispossible to inhibit abrasion and scratch of the coating film by brush,etc.

(f) Inner surface, etc. of tableware and can washer for shop use

In these applications, non-sticking property, stain-proofing propertyand hot water resistance of the non-sticking composite material of thepresent invention can be used particularly effectively.

(g) Inner surface, door inner surface, etc. of heating cabinet for shopuse

In these applications, non-sticking property, stain-proofing property,transparency and heat resistance of the non-sticking composite materialof the present invention can be used particularly effectively.

Further as the cooking apparatuses other than above, to which thenon-sticking composite material of the present invention can be usedpreferably, there can be raised the same ones as exemplified in theabove-mentioned Embodiment 1.

[2] Office automation-related appliances

In office automation-related appliances, in addition to parts wheretoner is used, there are many other portions which are apt to be easilydamaged by particularly adhesion of dusts, etc. Mentioned below arenon-restricted typical examples thereof.

(1) Electrophotographic copying machine, facsimile machine, wordprocessor, and other apparatuses with printer mechanism

The non-sticking composite material is suitable as a material used forparts, where toner is used or toner possibly adheres. Examples of suchparts are mentioned below.

{circle around (1+L )} Fixing roll

(a) For monochromatic printing

When the non-sticking composite material of the present invention whichcomprises the metallic substrate such as aluminum and SUS and is in theform of roll is used, a fixing roll having excellent non-stickingproperty against toner and heat resistance can be obtained. Since thecoating film of the present invention has excellent adhesive property,no primer need be provided, and processability in production isexcellent. Further the coating film has high surface hardness andexcellent durability such as abrasion resistance.

(b) For both monochromatic printing and color printing

Substrate: Metallic substrate coated with silicon rubber or urethanerubber and further with silicon oil for mold releasing

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating or in the form of tube or sheet

When the non-sticking composite material of the present invention isused, a fixing roll having excellent non-sticking property againsttoner, mold release property of paper and abrasion resistance can beobtained. Since the coating film of the present invention has excellentadhesive property, no primer need be provided, and processability inproduction is excellent.

{circle around (2+L )} Press roll (for both color and monochromaticprinting)

Substrate: Metallic substrate coated with silicon rubber or urethanerubber

When the non-sticking composite material of the present inventioncomprising the above-mentioned substrate is used, a press roll havingexcellent non-sticking property against toner and abrasion resistancecan be obtained. No primer need be provided for the coating film of thepresent invention, and processability in production is excellent becausethe coating film has good adhesive property.

{circle around (3+L )} Charged roll (for both color and monochromaticprinting)

Substrate: Urethane rubber-made substrate

When the non-sticking composite material of the present inventioncomprising the above-mentioned substrate is used, a charged roll havingexcellent non-sticking property against toner, mold release property ofpaper and abrasion resistance can be obtained. Since the coating film ofthe present invention has excellent adhesive property, no primer need beprovided, and processability in production is excellent.

{circle around (4+L )} Transfer roll (for both color and monochromaticprinting)

Substrate: Urethane rubber-made substrate

When the non-sticking composite material of the present inventioncomprising the above-mentioned substrate is used, a transfer roll havingexcellent non-sticking property against toner, mold release property ofpaper and abrasion resistance can be obtained. Since the coating film ofthe present invention has excellent adhesive property, no primer need beprovided, and processability in production is excellent.

{circle around (5+L )} Transfer belt (for both color and monochromaticprinting)

Substrate: Polyimide-made substrate

When the non-sticking composite material of the present inventioncomprising the above-mentioned substrate is used, a transfer belt havingexcellent non-sticking property against toner and abrasion resistancecan be obtained. Since the coating film of the present invention hasexcellent adhesive property, no primer need be provided, andprocessability in production is excellent.

{circle around (6+L )} Separating claw and fixing bearing (surface)

Substrate: Heat resistant resin-made substrate (for example, PPS,polyamideimide, polyether imide, POM, PEEK, or the like)

When the non-sticking composite material of the present inventioncomprising the above-mentioned substrate is used, a separating clawhaving excellent non-sticking property against toner, abrasionresistance and paper feed property and hardly injuring a roll and afixing bearing having low friction property and excellent abrasionresistance and heat resistance can be obtained. Since the coating filmof the present invention has excellent adhesive property, no primer needbe provided, and processability in production is excellent.

{circle around (7+L )} Paper delivery roll and paper delivery guide

Substrate: Resin-made substrate (for example, PPS, polyamideimide,polyether imide, POM, PEEK, or the like)

When the non-sticking composite material of the present inventioncomprising the above-mentioned substrate is used, a paper delivery rolland paper delivery guide having excellent non-sticking property againsttoner and abrasion resistance can be obtained. Since the coating film ofthe present invention has excellent adhesive property, no primer need beprovided, and processability in production is excellent.

Also the non-sticking composite material of the present invention can beused on the following parts for office automation-related apparatusesparticularly by making the use of its good transparency.

{circle around (8+L )} Cathode ray tube, liquid crystal panel and plasmadisplay (front surface)

When this non-sticking composite material is used, a cathode ray tube,liquid crystal panel and plasma display having excellent transparency,non-sticking property and stain-proofing property against dust,fingerprint, etc. can be obtained. No primer need be provided, andprocessability in production is excellent. Further the coating film hashigh surface hardness and excellent abrasion resistance and scratchresistance.

{circle around (9+L )} Contact glass (surface)

When the non-sticking composite material of the present invention isused, a contact glass having excellent transparency, non-stickingproperty and stain-proofing property against dust, fingerprint, etc.,and excellent non-sticking property against ink eraser, marking ink,etc. can be obtained. Since the coating film of the present inventionhas excellent adhesive property, no primer need be provided, andprocessability in production is excellent. Further the coating film hashigh surface hardness and excellent abrasion resistance and scratchresistance.

[3] Building material

There are also some building materials which require non-stickingproperty. Mentioned below are examples of such building materials andeffects exhibited in addition to non-sticking property.

{circle around (1+L )} Glass for building

Building glass, polished flat glass for building (window glass), windowof stained glass, windshield glass, light shielding ratio adjustableglass, etc.

In these applications, transparency, stain-proofing property and flameretardancy of the non-sticking composite material of the presentinvention can be particularly effectively exhibited.

{circle around (2+L )} Outer wall material, roofing material andinterior and exterior materials (made of metal)

(a) Exterior metallic building material for wall, metallic buildingmaterial, interior and exterior metallic panel for building, metallicfence, metallic tile, metallic building panel, etc.

(b) Metallic roofing material, solar system built-in roofing material,etc.

(c) Metallic door, metallic grating, metallic shutter, metallic fence,metallic porch (for building), etc.

(d) Metallic blind (for outdoor use), gutter, sash, rain door, etc.

(e) Metallic ceiling panel, metallic floor tile, metallic wall panelcoated with decorative vinyl chloride sheet, etc.

(f) Metallic parking facilities for cars, metallic object of art, etc.

In these applications, weather resistance, stain-proofing property andtransparency (property for exhibiting clear surface pattern) of thenon-sticking composite material of the present invention can be usedparticularly effectively.

{circle around (3+L )} Outer wall material, roofing material andinterior and exterior materials (non-metallic inorganic material)

(a) Segmental concrete block or concrete block bonded with a tile orsliced natural stone, segmental concrete road pavement board or concreteroad pavement board having a surface of rubber material and concreteboard which may be reinforced with GRC (fiber-reinforced concrete) wallmaterial, etc.

(b) Extrusion-molded cement such as cement having tile-like surface

(c) Building stone such as artificial stone

(d) Building tile, luster-finished tile, floor tile, ceramic tile andborder tile made of pottery

(e) Exterior material for building and for wall such as non-metallicexterior material for building, building material, building panel andwall tile for building

(f) Roofing material such as solar system built-in roofing material madeof ceramic

(g) Gravestone and grave-post

(h) Small sculpture, standing sculpture, image, bust and other object ofart made of stone, concrete or marble

In these applications, weather resistance, stain-proofing property,water-proofing property, transparency (property for exhibiting clearsurface pattern), processability and adhesive property of thenon-sticking composite material of the present invention, abrasionresistance thereof in case of above (c) and weathering preventingproperty thereof in cases of (g) and (h) can be used particularlyeffectively.

{circle around (4+L )} Outer wall material, roofing material andinterior and exterior materials (made of resin)

(a) Floor panel, ceiling panel, etc.

(b) Grating, gutter, blind and door including those for indoor use, etc.

(c) Plastic panel for concrete

(d) Gasket for building

(e) Curtain, cover, sunshield, etc. with an insect-proofing, ultravioletray and heat shielding and scatter preventing film

(f) Flooring material made of stone or flooring material made ofpolyvinyl chloride and having a surface of stone pattern

(g) Solar system built-in plastic roofing material

(h) Sectional polyvinyl chloride tile having clearance and being capableof draining water

(i) Synthetic resin sash

(j) Decorative board for counter, furniture, sill, wall panel,bucksplash, baseboard, and wall of bathroom and shower room

(k) Prefabricated assembly set for washstand, shower room, lavatory,transferable toilet, public toilet, etc.

(l) Prefabricated assembly set for sauna room, garage, etc.

In these applications, weather resistance, stain-proofing property,transparency (property for exhibiting clear surface pattern), waterresistance, processability and adhesive property of the non-stickingcomposite material of the present invention can be used particularlyeffectively.

{circle around (5+L )} Outer wall material and roofing material (made ofwood)

(a) Timber for household utensils, timber and decorative board forbuilding such as veneer and wooden panel, etc.

(b) Wooden fence, interior door and window frame, etc.

(c) Wooden panel for building produced by adhering elastic rubbermaterial on the back of plywood

(d) Wooden assembly set for building

In these applications, weather resistance, stain-proofing property,transparency (property for exhibiting clear surface pattern), waterresistance, processability and adhesive property of the non-stickingcomposite material of the present invention can be used particularlyeffectively.

{circle around (6+L )} Furniture

(a) Glass showcase, wagon, display wagon, display panel, display stand,meal conveying wagon, flower stand, etc.

(b) Shelf, screen, desk, sofa, shelf for chest of drawers, etc.

(c) Telephone booth made of metal or various materials

In these applications, stain-proofing property, transparency (propertyfor exhibiting clear surface pattern), water resistance andprocessability of the non-sticking composite material of the presentinvention and further property for preventing paper from being pasted,adhesive property and abrasion resistance thereof in case of above (c)can be used particularly effectively.

{circle around (7+L )} Apparatuses for household and shop uses

(a) Gas oven with grill, range hood, ventilation hood, etc.

(b) Metallic duct for central heating, ventilator, air conditioner, etc.

In these applications, stain-proofing property, processability andadhesive property of the non-sticking composite material of the presentinvention can be used particularly effectively.

{circle around (8+L )} Housing facilities and apparatuses

(a) Coordinated kitchen units including kitchen range (oven), sink, etc.

(b) Electrically heated, gas heated and oil heated water heaters(including instantaneous water heater)

(c) Wall-mounted washbasin, washstand, hair washing appliance fordomestic use, washstand with hair washing function, washbasin forwashstand, washbasin with cover, bow window type washstand, etc.

(d) Flush toilet stool, small size chamber pot for car, urinal, toiletstool with urinalyzer, toilet stool for little children, toilet stoolwith hot water washing function, toilet seat with deodorizing unit andwater tank for flush toilet

In these applications, stain-proofing property, property for exhibitingclear surface pattern (transparency), processability, abrasionresistance and anti-bacterial property of the non-sticking compositematerial of the present invention can be used particularly effectively.

(e) Lining for bathrooms including shower room, sauna bath for domesticand shop uses, bath tubs such as prefabricated bath tub, bath tub withbubble generator and bath utensils such as handle mounted on bath tuband soap holder

(f) Escalator, elevator (including those for private houses), etc.

In these applications, stain-proofing property, property for exhibitingclear surface pattern (transparency) and processability of thenon-sticking composite material of the present invention, heatresistance thereof in cases of above (a), (b) and (e), abrasionresistance thereof in cases of above (c) to (e) and sliding property andrust preventing property thereof in case of above (f) can be usedparticularly effectively.

{circle around (9+L )} Construction

(a) Sign for bus stop, sign for street, sign mounted on guardrail, etc.

(b) Signals such as luminous signal and mechanical signal

(c) Guardrail produced by using various materials

(d) Utility pole produced by using various materials

(e) Sound-proof wall

(f) Plastic molding panel for concrete for building and construction,etc.

In these applications, weather resistance, stain-proofing property,transparency, processability and adhesive property of the non-stickingcomposite material of the present invention and further mold-releaseproperty thereof in case of above (f) can be used particularlyeffectively.

[4] Household electric appliances (excluding cooking apparatuses)

In household electric appliances excluding cooking apparatuses, thereare many parts thereof which require non-sticking property againstdusts, oil, etc. Typical examples thereof are mentioned below.

{circle around (1+L )} Ventilation fan (fan, frame, cover, etc.)

Substrate: Resin (PP, etc.), aluminum, galvanized steel sheet,galvanized steel plate, etc.

When the non-sticking composite material of the present inventioncomprising the above-mentioned substrate is used, excellent non-stickingproperty and removing property against oil stain, cohering stain, etc.can be effectively utilized. Particularly the coating film is excellentin transparency and property for exhibiting clear surface pattern, andabrasion and scratching resulting from cleaning with a brush, etc. canbe inhibited.

{circle around (2+L )} Air conditioner (louver and filter of indoorunit, exterior, louver and propeller of outdoor unit, etc.)

Substrate: Resin (PP, etc.), aluminum, galvanized steel sheet,galvanized steel plate

When the non-sticking composite material of the present inventioncomprising the above-mentioned substrate is used, excellent non-stickingproperty and removing property against stains such as dusts, soots andnicotine can be effectively utilized. Particularly transparency,property for exhibiting clear surface pattern and processability can beimproved.

{circle around (3+L )} Refrigerator (inside and outside surfaces)

Substrate: Resin (PP), aluminum, SUS, galvanized steel, sheet,galvanized steel plate, etc.

When the non-sticking composite material of the present inventioncomprising the above-mentioned substrate is used, excellent non-stickingproperty and removing property against foods, seasoning, coheringstains, etc. can be effectively utilized. Particularly transparency,property for exhibiting clear surface pattern and processability can beimproved.

EMBODIMENT 4 (Weather resistant composite material)

With respect to building materials such as building glass, variousinterior and exterior wall materials, roofing materials and interior andexterior materials and construction-related materials such as sign,signal, guardrail, utility pole and sound-proof wall, since they areused exposed to environment, the surfaces thereof have been required tohave weather resistance particularly and, stain-proofing propertyagainst dust, exhaust gas and rain water, transparency and property forexhibiting clear surface pattern. The substrates for these buildingmaterials are made of glass, metal, ceramic, synthetic resin orconcrete. Some of them are not subjected to any treatment on theirsurfaces, but to cope with the mentioned requirement, to a surface ofthe composite materials used for these building materials is applied afluorine-containing polymer having excellent weather resistance, heatresistance, chemical resistance, corrosion resistance, surfacecharacteristics (non-sticking property, low friction property, etc.),electric insulating property, etc. However since the fluorine-containingpolymer has not enough adhesion to a surface of substrate such as metaldue to its excellent non-sticking property, it is necessary to (1) usean adhesive or (2) to carry out, on a surface of the substrate,sand-blasting or electrochemical etching to make the surface rough foradhering by anchor effect.

However it is not possible to make the best use of transparency of aglass material and color tone such as metal gloss of a metallicsubstrate, and thus there is a problem with property for exhibitingclear surface pattern, since in the method of using an adhesive in above(1), no transparent adhesive having high adhesion and heat resistance isnot available and also since in the method of roughening the surface ofsubstrate in above (2), the surface is significantly roughened. Furthereven if a transparent adhesive is developed, since a fluorine-containingpolymer contained in the coating film on the surface of the buildingmaterial is in general soft, when it is applied to an exterior buildingmaterial, etc., foreign matters, dusts and stains easily enter thecoating film and therefore cause staining easily. Also the stains aredifficult to be removed, and thus transparency is lowered and surfacepattern of a substrate becomes unclear.

To solve that, an attempt to endow the coating film comprising thefluorine-containing polymer with hardness by adding a glassy oraluminum-based inorganic filler has been made, but there was a problemthat the coating film became fragile, transparency was lowered andsurface pattern of a substrate became unclear.

Also various studies for giving water-repellency to glass have been madefor the purpose to repel rain water on a window glass or fender mirrorof car and make field of view good in rainy days. It is considered thatthe results of such studies are used in the fields requiring weatherresistance.

In this regard, there are proposals as cited above (JP-A-4-124047,JP-A-4-325446, JP-A-5-24885, JP-A-4-359086, JP-A-5-170486,JP-A-5-213633, JP-A-5-51238, JP-A-6-329442, JP-A-6-340451,JP-A-7-102207, and JP-A-7-157335).

However as mentioned above, even by those conventional sol-gel methods,a weather resistant coating film having excellent transparency, abrasionresistance, heat resistance, water- and oil-repellency and scratchresistance has not been obtained.

The weather resistant composite material obtained by applying thecoating composition of the present invention to a substrate can be usedfor various appliances, utensils and building materials firstly becauseexcellent weather resistance can be maintained for a long period oftime, secondly because the fine particles of the fluorine-containingethylenic polymer (A) having functional group are uniformly dispersed inthe coating film comprising the metal oxide (B) due to their goodinterfacial adhesion and the coating film has enough hardness,transparency and adhesive property, and thirdly because the coating filmcomprising the fluorine-containing ethylenic polymer (A) havingfunctional group and metal oxide (B) has good heat resistance, abrasionresistance, scratch resistance, stain-proofing property,water-repellency, anti-bacterial property, etc.

The present invention can provide the weather resistant compositematerial comprising a substrate and, on a surface of the substrate, acoating film which comprises fine particles of the fluorine-containingethylenic polymer (A) having functional group prepared by copolymerizing

(a) 0.05 to 50% by mole of at least one of fluorine-containing ethylenicmonomers having at least one functional group selected from hydroxyl,carboxyl, a carboxylic salt group, a carboxylic ester group and epoxyand

(b) 50 to 99.95% by mole of at least one of fluorine-containingethylenic monomers having no functional group mentioned above and themetal oxide (B); the fine particles of the polymer (A) are contained indispersed state in the metal oxide (B) layer.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the fluorine-containing ethylenicmonomer (a) having functional group is at least one offluorine-containing ethylenic monomers having functional group andrepresented by the formula (1):

CX₂═CX¹—R_(f)—Y  (1)

wherein Y is —CH₂OH, —COOH, a carboxylic salt group, a carboxylic estergroup or epoxy, X and X¹ are the same or different and each is hydrogenatom or fluorine atom, R_(f) is a divalent fluorine-containing alkylenegroup having 1 to 40 carbon atoms, a fluorine-containing oxyalkylenegroup having 1 to 40 carbon atoms, a fluorine-containing alkylene grouphaving ether group and 1 to 40 carbon atoms or a fluorine-containingoxyalkylene group having ether bond and 1 to 40 carbon atoms.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the fluorine-containing ethylenicpolymer (A) having functional group is the above-mentioned polymer (I).

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the fluorine-containing ethylenicpolymer (A) having functional group is the above-mentioned polymer (II).

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the fluorine-containing ethylenicpolymer (A) having functional group is the above-mentioned polymer(III).

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the metal oxide (B) is a siliconoxide.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the metal oxide (B) is analuminum oxide.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the metal oxide (B) is a titaniumoxide.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the substrate is a metallicsubstrate.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the substrate is a non-metallicinorganic substrate.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the substrate is a glasssubstrate.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the substrate is a concretesubstrate.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the substrate is a cementsubstrate.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the substrate is a tilesubstrate.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the substrate is a ceramicsubstrate.

Also the present invention can provide the above-mentioned weatherresistant composite material, in which the substrate is a syntheticresin substrate.

In principle the above-mentioned descriptions regarding the coatingcomposition, coating film and methods for production thereof are appliedto the weather resistant composite material of the present invention.Explained below are particularly preferable embodiments thereof.

Examples of the substrate usually used for the weather resistantcomposite material of the present invention are metallic plates ofaluminum, stainless steel, iron and titanium; metallic plates subjectedto hot-dip zinc plating, aluminum plating, etc.; metallic platessubjected to chemical conversion treatment such as oxidation withchromic acid, phosphoric acid, etc.; alumite-treated metallic platessubjected to anodizing; and the like.

Examples of the non-metallic inorganic substrate used usually are glasssubstrates such as crystallized glass, foam glass, heat reflectingglass, heat absorbing glass and multi-layered glass; ceramic substratessuch as tile, large size pottery board, ceramic panel and brick; naturalstones such as granite and marble; concrete substrates such as highstrength concrete, glass fiber-reinforced concrete (GRC), carbonfiber-reinforced concrete (CFRC), lightweight aerated concrete (ALC) andcomposite ALC; cement substrates such as extrusion molded cement andcomposite molded cement; asbestos slate; enamelled steel plate; and thelike.

Further examples of the synthetic resin substrate used arepolycarbonate, polyester resin, acrylic resin, vinyl chloride resin,artificial marble (mainly comprising unsaturated polyester resin oracrylic resin), steel plates coated with vinyl chloride resin, acrylicresin or urethane resin, and the like.

Among them, where transparency is required, the non-metallic inorganicsubstrate of glass and the synthetic resin substrate of acrylic resinand polycarbonate are usually used.

A thickness of the metal oxide coating film of the above-mentionedweather resistant composite material of the present invention variesdepending on kind and portion of appliances and utensils to which thefilm is applied. The thickness is from 0.01 to 100 μm, preferably from0.1 to 70 μm, particularly preferably from 1 to 50 μm.

Appliances, utensils, building materials and portions thereof where theweather resistant composite material of the present invention can beused are raised and classified below by the fields applied, but are notlimited to them.

[1] Building material

Building materials are exposed to the sun and weather, and thereforemany of them require weather resistance. Mentioned below are examples ofbuilding materials and effects exhibited in addition to weatherresistance.

{circle around (1)} Glass for building

Building glass, polished flat glass for building (window glass), windowof stained glass, windshield glass, light shielding ratio adjustableglass, etc.

In these applications, transparency, stain-proofing property and flameretardancy of the weather resistant composite material of the presentinvention can be used particularly effectively.

{circle around (2)} Outer wall material, roofing material and exteriormaterials (made of metal)

(a) Exterior metallic building material for wall, metallic buildingmaterial, exterior metal panel for building, metallic fence, metallictile, metallic building panel, etc.

(b) Metallic roofing material, solar system built-in roofing material,etc.

(c) Metallic door, metallic grating, metallic shutter, metallic fence,metallic porch (for building), etc.

(d) Metallic blind (for outdoor use), gutter, sash, rain door, etc.

(e) Metallic ceiling panel, metallic floor tile, metallic wall panelcoated with decorative vinyl chloride sheet, etc.

(f) Metallic parking facilities for cars, metallic object of art, etc.

In these applications, non-sticking property, stain-proofing propertyand transparency (property for exhibiting clear surface pattern) of theweather resistant composite material of the present invention can beused particularly effectively.

{circle around (3)} Outer wall material, roofing material and exteriormaterial (non-metallic inorganic material)

(a) Segmental concrete block or concrete block bonded with a tile orsliced natural stone, segmental concrete road pavement board andconcrete road pavement board having a surface of rubber material andconcrete board which may be reinforced with GRC (fiber-reinforcedconcrete) wall material, etc.

(b) Extrusion-molded cement such as cement having tile-like surface

(c) Building stone such as artificial stone

(d) Building tile, luster-finished tile, floor tile, ceramic tile andborder tile made of pottery

(e) Non-metallic exterior material for building and for wall such asexterior material for building, building material, building panel andwall tile for building

(f) Roofing material such as solar system built-in roofing material madeof ceramic

(g) Gravestone and grave post

(h) Small sculpture, standing sculpture, image, bust and other object ofart made of stone, concrete or marble

In these applications, non-sticking property, stain-proofing property,water-proofing property, transparency (property for exhibiting clearsurface pattern), processability and adhesive property of the weatherresistant composite material of the present invention, abrasionresistance thereof in case of above (c) and weathering preventingproperty thereof in cases of (g) and (h) can be used particularlyeffectively.

{circle around (4)} Outer wall material, roofing material and exteriormaterial (made of resin)

(a) Floor panel, ceiling panel, etc.

(b) Grating, gutter, blind and door including those for indoor use, etc.

(c) Plastic panel for concrete

(d) Gasket for building

(e) Curtain, cover, sunshield, etc. with an insect-proofing, ultravioletray and heat shielding and scatter preventing film

(f) Flooring material made of stone or flooring material made ofpolyvinyl chloride and having a surface of stone pattern

(g) Solar system built-in plastic roofing material

(h) Sectional polyvinyl chloride tile having clearance and being capableof draining water

(i) Synthetic resin sash

In these applications, non-sticking property, stain-proofing property,transparency (property for exhibiting clear surface pattern), waterresistance, processability and adhesive property of the weatherresistant composite material of the present invention can be usedparticularly effectively.

{circle around (5)} Outer wall material and roofing material (made ofwood)

(a) Timber for household utensils, timber and decorative board forbuilding such as veneer and wooden panel, etc.

(b) Wooden fence, interior door and window frame, etc.

(c) Wooden material for building produced by adhering elastic rubbermaterial on the back of plywood

(d) Wooden assembly set for building

In these applications, non-sticking property, stain-proofing property,transparency (property for exhibiting clear surface pattern), waterresistance, processability and adhesive property of the weatherresistant composite material of the present invention can be usedparticularly effectively.

{circle around (6)} Construction

(a) Sign for bus stop, sign for street, sign mounted on guardrail, etc.

(b) Signals such as luminous signal and mechanical signal

(c) Guardrail produced by using various materials

(d) Utility pole produced by using various materials

(e) Sound-proof wall

(f) Plastic molding pane for concrete for building and construction,etc.

In these applications, weather resistance, stain-proofing property,transparency, processability and adhesive property of the weatherresistant composite material of the present invention and furthermold-release property thereof in case of above (f) can be usedparticularly effectively.

[2] Solar battery

In the field of solar batteries, since they are used continuously beingexposed to the sun and weather, both the whole solar battery module andparts thereof require weather resistance. Mentioned below are examplesof the parts of solar batteries to which the weather resistant compositematerial of the present invention can be applied, and effects exhibitedin addition to weather resistance.

{circle around (1)} Cover for solar battery

Application: Outermost surface

Substrate: Amorphous silicon, monocrystal, polycrystal silicon, fillerlayer (EVA, glass, etc.)

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Transparency, weather resistance, stain-proofing property, flameretardancy

[3] Car

With respect to car-related parts, too, since exterior materials such asbody and glass are exposed to the sun and weather like the buildingmaterials, weather resistance is required for them. Mentioned below areexamples of car-related applications and effects exhibited in additionto weather resistance.

{circle around (1)} Car and train

Application: Body

Substrate: Coated surfaces of steel plate, other metal, acrylic resin,etc.

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating or in the form of film

Effect: Processability, transparency, property for exhibiting clearsurface pattern, stain-proofing property, stain removing property

{circle around (2)} Glass for car and train

Application: Window, windshield, rear glass, side window

Substrate: Glass

Fluorine-containing polymer having functional group: I, II, II

Applying method: Coating or in the form of film

Effect: Transparency, processability, stain-proofing property, stainremoving property, water-repellency, scatter preventing property

{circle around (3)} Lights (headlight, taillight, turn signal)

Application: Surface of cover, bulb surface

Substrate: Glass, polycarbonate

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating or in the form of film

Effect: Weather resistance, stain-proofing property, processability,water-repellency,

{circle around (4)} Wheel

Application: Surface

Substrate: Aluminum, cast iron, resin (PP, ABS, PC, PPE, alloys)

Fluorine-containing polymer having functional group: I, II, III

Applying method: Coating

Effect: Weather resistance, stain-proofing property, transparency,property for exhibiting clear surface pattern, processability

[4] Others

{circle around (1)} Insulators and pantograph

Application: Surface

Substrate: Ceramic

Fluorine-containing polymer having functional group: I, I, III

Applying method: Coating

Effect: Processability, weather resistance, stain-proofing property

EMBODIMENT 5 (Composite Material Having Sliding Property)

In the field of domestic appliances, since, for example, a flat iron isused with its heating surface being pressed and slided on clothes,so-called sliding properties such as low friction property and abrasionresistance are required and it has been desired to use materials havingexcellent sliding properties for such applications.

To satisfy such requirement, for example, a fluorine-containing polymerhaving excellent sliding properties such as low friction property, heatresistance, chemical resistance, corrosion resistance, weatherresistance, non-sticking property, electric insulating property, etc.has been applied to a heating surface of a flat iron, etc. However thefluorine-containing polymer has insufficient adhesion to a metal surfacedue to its excellent non-sticking property. Therefore it is necessary to(1) use an adhesive or (2) carry out sand-blasting or etching byelectrochemical method on a surface of a substrate to make the surfacerough for adhering by anchor effect.

However it is not possible to make the best use of transparency of aglass substrate and color tone of a metallic substrate and thus there isa problem with property for exhibiting clear surface pattern, since inthe method using an adhesive like the method (1), no transparentadhesive having heat resistance and high adhesive property is available,and also since in the method for making the substrate surface rough likethe method (2), the substrate surface is made rough significantly.Further even if a transparent adhesive is developed, since afluorine-containing polymer composing a coating film on a slidingsurface is soft, for example, due to friction and abrasion during longterm use, the coating film on a sliding surface is injured and thustransparency is lowered and a surface pattern of a substrate becomesunclear, or due to abrasion, inherent sliding properties (low frictionproperty), non-sticking property and water-repellency of afluorine-containing polymer are lowered.

To prevent them, there have been made trials to endow the coating filmcomprising a fluorine-containing polymer with hardness by adding aglassy or aluminum-based inorganic filler. However there were problemsthat the coating film became fragile, transparency was lowered and asurface pattern of a substrate became unclear.

Also for the purpose to repel rain water attached to a window glass andfender mirror of a car in rainy days and make field of view clear,various studies have been made to give water-repellency to glass, and ithas been considered to use the results thereof in the fields requiringsliding properties (low friction property).

Accordingly, the above-mentioned proposals have been made (inJP-A-4-124047, JP-A-4-325446, JP-A-5-24885, JP-A-4-359086,JP-A-5-170486, JP-A-5-213633, JP-A-5-51238, JP-A-6-329442,JP-A-6-340451, JP-A-7-102207, JP-A-7-157335).

However as mentioned above, even by these conventional sol-gel methods,coating films having excellent transparency, heat resistance, water- andoil-repellency, scratch resistance and sliding properties such as lowfriction property and abrasion resistance have not been obtained.

The composite material having sliding property which is obtained byapplying the coating composition of the present invention to thesubstrate can be used on various appliances, utensils, etc. firstlybecause excellent sliding property can be maintained for a long periodof time, secondly because fine particles of the fluorine-containingethylenic polymer (A) having functional group are dispersed uniformlybecause of their good interfacial adhesion in the coating filmcomprising the metal oxide (B) and the coating film has enough hardness,transparency and adhesive property, and thirdly because the coating filmcomprising the fluorine-containing ethylenic polymer (A) havingfunctional group and the metal oxide (B) has good heat resistance,scratch resistance, stain-proofing property, water-repellency andanti-bacterial property.

The present invention can provide a composite material having slidingproperty produced by applying, on a surface of the substrate, a coatingfilm which comprises the metal oxide (B) and the fine particles of thefluorine-containing ethylenic polymer (A) having functional groupprepared by copolymerizing:

(a) 0.05 to 50% by mole of at least one of fluorine-containing ethylenicmonomers having at least one functional group selected from the groupconsisting of hydroxyl, carboxyl, a carboxylic salt group, a carboxylicester group and epoxy, and

(b) 50 to 99.95% by mole of a fluorine-containing ethylenic monomerhaving no functional group mentioned above; the fine particles of thepolymer (A) are contained in dispersed state in the metal oxide (B)layer.

Also the present invention can provide a composite material havingsliding property, in which the above-mentioned fluorine-containingethylenic monomer (a) having functional group is at least one offluorine-containing ethylenic monomers having functional group andrepresented by the formula (1):

CX₂═CX¹—R_(f)—Y   (1)

wherein Y is —CH₂OH, —COOH, a carboxylic salt group, a carboxylic estergroup or epoxy, X and X¹ are the same or different and each is hydrogenatom or fluorine atom, R_(f) is a divalent fluorine-containing alkylenegroup having 1 to 40 carbon atoms, a fluorine-containing oxalkylenegroup having 1 to 40 carbon atoms, a fluorine-containing alkylene grouphaving ether group and 1 to 40 carbon atoms or a fluorine-containingoxyalkylene group having ether bond and 1 to 40 carbon atoms.

Also the present invention can provide the composite material havingsliding property, in which the above-mentioned fluorine-containingpolymer (A) having functional group is the polymer (I).

Also the present invention can provide the composite material havingsliding property, in which the above-mentioned fluorine-containingpolymer (A) having functional group is the polymer (II).

Also the present invention can provide the composite material havingsliding property, in which the above-mentioned metal oxide (B) is asilicon oxide.

Also the present invention can provide the composite material havingsliding property, in which the above-mentioned metal oxide (B) is analuminum oxide.

Also the present invention can provide the composite material havingsliding property, in which the above-mentioned metal oxide (B) is atitanium oxide.

Also the present invention can provide the composite material havingsliding property, in which the above-mentioned substrate is a metallicsubstrate.

Also the present invention can provide the composite material havingsliding property, in which the above-mentioned substrate is a glasssubstrate.

Also the present invention can provide the composite material havingsliding property, in which the above-mentioned substrate is a syntheticresin substrate.

Also the present invention can provide the composite material havingsliding property, in which the above-mentioned substrate is a ceramicsubstrate.

In principle the above-mentioned descriptions regarding the coatingcomposition, coating film and methods for production thereof are appliedto the composite material having sliding property of the presentinvention. Explained below are particularly preferable embodimentsthereof.

As the substrate for the composite material having sliding property ofthe present invention, all the substrates mentioned above can be used.Examples of the substrate used particularly widely as a metallicsubstrate are, for instance,

{circle around (1)} cold rolled steel sheet,

{circle around (2)} plated steel sheet, for example, Zn-plated steelsheet, Zn alloy-plated steel sheet, Al-plated steel sheet, Alalloy-plated steel sheet, Cr-plated steel sheet (TFS), Ni-plated steelsheet, Cu-plated steel sheet, galvanized steel sheet, etc.,

{circle around (3)} aluminum sheet,

{circle around (4)} titanium sheet,

{circle around (5)} stainless steel sheet, and the like.

In addition, where transparency is required, the ceramic substrate ofglass and the resin substrate of acrylic resin and polycarbonate areusually used.

A thickness of the metal oxide coating film of the composite materialhaving sliding property of the present invention varies depending onkind and portion of appliances and utensils to which the film isapplied. The thickness is from 0.01 to 100 μm, preferably from 0.01 to50 μm, particularly preferably from 0.02 to 20 μm.

Mentioned below are non-restricted examples of appliances, utensils andparts thereof, to which the composite material having sliding propertyof the present invention can be suitably used. Those appliances,utensils and parts thereof are classified by fields they belong to.

[1] Office automation-related apparatuses

In office automation-related apparatuses, there are many parts such asparts contacting feeding paper, which are desired to have excellentsliding properties such as abrasion resistance and low frictionproperty. Mentioned below are non-restricted examples thereof andeffects exhibited in addition to the sliding property.

{circle around (2)} Electrophotographic copying machine, facsimilemachine

The composite material having sliding property is suitable as a materialused for parts for feeding paper. Examples of such parts are mentionedbelow.

(a) Separating claw and fixing bearing (surface)

Substrate: Heat resistant resin-made substrate (for example, PPS,polyamideimide, polyether imide, POM, PEEK, or the like)

Fluorine-containing polymer having functional group: I, II

Applying method: Coating

When this composite material having sliding property is used, aseparating claw having excellent non-sticking property against toner,abrasion resistance and paper feed property and hardly injuring a rolland a fixing bearing having low friction property and excellent abrasionresistance and heat resistance can be obtained. Since thefluorine-containing polymer having functional group has excellentadhesive property, no primer need be provided, and processability inproduction is excellent.

(b) Paper delivery roll and paper delivery guide

Substrate: Resin-made substrate (for example, polyether sulfide,polyamideimide, polyether imide, POM, PEEK, or the like)

Fluorine-containing polymer having functional group: I, II

Applying method: Coating

When the composite material having sliding property of the presentinvention is used, a paper delivery roll and paper delivery guide havingexcellent non-sticking property for toner and abrasion resistance can beobtained. Since the fluorine-containing polymer having functional grouphas excellent adhesive property, no primer need be provided, andprocessability in production is excellent.

[2] Domestic electric appliances

With respect to domestic electric appliances, there are many partsthereof which are desired to have sliding properties including abrasionresistance, etc. Mentioned below are examples of the domestic applianceand effects exhibited in addition to the sliding properties. Accordinglythe present invention also relates to these parts and domestic electricappliances.

{circle around (1)} Flat iron

Application: Heating surface

Substrate: SUS, steel plate

Fluorine-containing polymer having functional group: I, II

Applying method: Coating

In these applications, heat resistance, processability and property forexhibiting clear surface pattern which the composite material havingsliding property of the present invention possesses can be usedparticularly effectively.

[3] Housing facilities and equipment

In the housing facilities and equipment, too, since easy handling whenused is desired, there are many parts which are required to have slidingproperties including abrasion resistance and low friction property.Mentioned below are examples of the housing facilities and equipment andparts thereof and also effects exhibited in addition to the slidingproperties. Accordingly the present invention also relates to thesehousing facilities and equipment and parts thereof.

{circle around (1)} Escalator

Application: Surface of skirt (prevention from being caught into amachine)

Substrate: SUS, steel plate

Fluorine-containing polymer having functional group: I, II

Applying method: Coating

In these applications, processability, property for exhibiting clearsurface pattern and weather resistance which the composite materialhaving sliding property of the present invention possesses can be usedparticularly effectively.

[4] Cars

In engines and gears of cars, there are many parts which are required tohave sliding properties, heat resistance and chemical resistance.

{circle around (1)} Rotary engine

Application: Inner wall

Substrate: Aluminum, steel plate

Fluorine-containing polymer having functional group: I, II

Applying method: Coating

In these applications, processability, heat resistance, non-stickingproperty and stain-proofing property which the composite material havingsliding property of the present invention possesses can be usedparticularly effectively.

{circle around (2)} Piston, piston ring

Application: Surface

Substrate: Aluminum, steel plate

Fluorine-containing polymer having functional group: I, II

Applying method: Coating

In these applications, processability and heat resistance which thecomposite material having sliding property of the present inventionpossesses can be used particularly effectively.

{circle around (3)} Throttle shaft

Application: Surface

Substrate: Aluminum, iron-based metal

Fluorine-containing polymer having functional group: I, II

Applying method: Coating

In these applications, processability and heat resistance which thecomposite material having sliding property of the present inventionpossesses can be used particularly effectively.

In addition, the composite material having sliding property of thepresent invention can give sliding property on steering, hinge pin,gears, brake shoe, bearing retainer, etc. when applied to the surfacesthereof in the form of coating.

[5] Others

{circle around (1)} Bolts and nuts

Application: Surface

Substrate: Iron

Fluorine-containing polymer having functional group: I, II

Applying method: Coating

In these applications, processability, rust-proofing property, chemicalresistance and workability at low torque which the composite materialhaving sliding property of the present invention possesses can be usedparticularly effectively.

{circle around (2)} Cutlery such as scissors, saw and knife

Application: Surface of edge

Substrate: Iron

Fluorine-containing polymer having functional group: I, II

Applying method: Coating

In these applications, non-sticking property, stain-proofing property,processability and cutting capability at low load which the compositematerial having sliding property of the present invention possesses canbe used particularly effectively.

{circle around (3)} Parts for pump

Application: Inner surface and outer surface of plunger, gear surface

Substrate: Aluminum, iron

Fluorine-containing polymer having functional group: I, II

Applying method: Coating, film

In these applications, chemical resistance, processability and abrasionresistance which the composite material having sliding property of thepresent invention possesses can be used particularly effectively.

{circle around (4)} Parts for air conditioner (car air conditioner, roomair conditioner, etc.)

Application: Piston ring, tip seal

Substrate: Aluminum, iron

Fluorine-containing polymer having functional group: I, II

Applying method: Coating

In these applications, processability and chemical resistance which thecomposite material having sliding property of the present inventionpossesses can be used particularly effectively.

In addition, the composite material having sliding property of thepresent invention can be applied to parts for vending machine, parts forcamera, parts for medical apparatuses (gastocamera, etc.), parts forclock, parts for agricultural machines, oilless bearing for mechanicalindustry, etc.

EMBODIMENT 6 (Composite Material for Cooking Apparatuses)

With respect to cooking apparatuses represented by griddle and ricecooker, it is desired that cooking can be done at higher temperature forshortening of cooking time and to pursue good taste of cooked dishes.Also it is desired that stains such as oil and scorch can be easilyremoved so as to clean these apparatuses after the cooking and that thesurfaces of the apparatuses are free from scratches by cleaning with abrush, spatula, etc. during long term use. Further good property forexhibiting clear surface pattern is also desired from the viewpoint ofappearance thereof.

In order to meet such requirement, as the composite material used forcooking apparatuses, a fluorine-containing polymer which is excellent inheat resistance, chemical resistance, corrosion resistance, weatherresistance, surface properties (non-sticking property, low frictionproperty, etc.) and electric insulating property is used on a heatingsurface of cooking apparatuses such as rice cooker or electric griddle.However the fluorine-containing polymer has insufficient adhesion to ametal surface due to its excellent non-sticking property. Therefore itis necessary to (1) use an adhesive or (2) carry out, on a surface of asubstrate, sand-blasting or etching by electrochemical method to makethe surface rough for adhering by anchor effect.

However it is not possible to make the best use of transparency of aglass substrate and color tone of a metallic substrate and thus there isa problem with property for exhibiting clear surface pattern, since inthe method using an adhesive like the method (1), no transparentadhesive having heat resistance and high adhesion is available, and alsosince in the method for making the substrate surface rough like themethod (2), the substrate surface is made rough significantly. Furthereven if a transparent adhesive is developed, since a fluorine-containingpolymer composing a coating film on a heating surface of cookingapparatuses, etc. is soft, for example, due to long term use or bycleaning with a spatula or brush, the coating film on a heating surfaceis injured and thus transparency is lowered and a surface pattern of asubstrate becomes unclear, or for example, due to abrasion, inherentnon-sticking property and water-repellency of a fluorine-containingpolymer are lowered.

To solve them, there have been made trials to endow the coating filmcomprising fluorine-containing polymer with hardness by adding a glassyor aluminum-based inorganic filler. However there were problems that thecoating film became fragile, transparency was lowered and a surfacepattern of a substrate became unclear.

To cope with these problems, the proposals have been made (inJP-A-4-124047, JP-A-4-325446, JP-A-5-24885, JP-A-4-359086,JP-A-5-170486, JP-A-5-213633, JP-A-5-51238, JP-A-6-329442,JP-A-6-340451, JP-A-7-102207, JP-A-7-157335).

However as mentioned above, even by these conventional sol-gel methods,coating films having excellent transparency, abrasion resistance, heatresistance, oil- and water-repellency and scratch resistance have notbeen obtained.

The composite material for cooking apparatuses which is obtained byapplying the coating composition of the present invention to thesubstrate can be used on various cooking apparatuses firstly becausefine particles of the fluorine-containing ethylenic polymer (A) havingfunctional group are dispersed uniformly because of their goodinterfacial adhesivity in the coating film comprising the metal oxide(B) and the coating film has enough hardness, transparency and adhesiveproperty, and secondly because the coating film comprising thefluorine-containing ethylenic polymer (A) having functional group andthe metal oxide (B) has good non-sticking property, heat resistance,abrasion resistance, scratch resistance, stain-proofing property,water-repellency and anti-bacterial property.

The present invention can provide the composite material for cookingapparatuses comprising a substrate and a coating film thereon whichcomprises the metal oxide (B) and the fine particles of thefluorine-containing ethylenic polymer (A) having functional groupprepared by copolymerizing:

(a) 0.05 to 50% by mole of at least one of fluorine-containing ethylenicmonomers having at least one functional group selected from the groupconsisting of hydroxyl, carboxyl, a carboxylic salt group, a carboxylicester group and epoxy, and

(b) 50 to 99.95% by mole of at least one of fluorine-containingethylenic monomers having no functional group mentioned above; the fineparticles of the polymer (A) are contained in dispersed state in themetal oxide (B) layer.

Also the present invention can provide the composite material, in whichthe above-mentioned fluorine-containing ethylenic monomer (a) havingfunctional group is at least one of fluorine-containing ethylenicmonomers having functional group and represented by the formula (1):

CX₂═CX¹—R_(f)—Y   (1)

wherein Y is —CH₂OH, —COOH, a carboxylic salt group, a carboxylic estergroup or epoxy, X and X¹ are the same or different and each is hydrogenatom or fluorine atom, R_(f) is a divalent fluorine-containing alkylenegroup having 1 to 40 carbon atoms, a fluorine-containing oxyalkylenegroup having 1 to 40 carbon atoms, a fluorine-containing alkylene grouphaving ether group and 1 to 40 carbon atoms or a fluorine-containingoxyalkylene group having ether bond and 1 to 40 carbon atoms.

Also the present invention can provide the composite material forcooking apparatuses, in which the above-mentioned fluorine-containingpolymer (A) having functional group is the polymer (I).

Also the present invention can provide the composite material forcooking apparatuses, in which the above-mentioned fluorine-containingpolymer (A) having functional group is the polymer (II).

Also the present invention can provide the composite material forcooking apparatuses, in which the above-mentioned fluorine-containingpolymer (A) having functional group is the polymer (III).

Also the present invention can provide the composite material forcooking apparatuses, in which the above-mentioned metal oxide (B) is asilicon oxide.

Also the present invention can provide the composite material for cookinapparatuses, in which the above-mentioned metal oxide (B) is an aluminumoxide.

Also the present invention can provide the composite material forcooking apparatuses, in which the above-mentioned metal oxide (B) is atitanium oxide.

Also the present invention can provide the composite material forcooking apparatuses, in which the above-mentioned substrate is ametallic substrate.

Also the present invention can provide the composite material forcooking apparatuses, in which the above-mentioned substrate is a glasssubstrate.

Also the present invention can provide the composite material forcooking apparatuses, in which the above-mentioned substrate is asynthetic resin substrate.

Also the present invention can provide the composite material forcooking apparatuses, in which the above-mentioned substrate is a ceramicsubstrate.

Also the present invention can provide cooking apparatuses produced byusing the composite material for cooking apparatuses.

Also the present invention can provide heating apparatuses for cookingproduced by using the composite material for cooking apparatuses.

Also the present invention can provide a griddle produced by using thecomposite material for cooking apparatuses.

Also the present invention can provide a griddle produced by applyingthe composite material for cooking apparatuses to its heating surfacemade of metal.

Also the present invention can provide a griddle produced by applyingthe composite material for cooking apparatuses to its glass lid.

Also the present invention can provide a range with oven produced byusing the composite material for cooking apparatuses.

Also the present invention can provide a range with oven produced byapplying the composite material for cooking apparatuses to its innersurface made of metal.

Also the present invention can provide a range with oven produced byusing the composite material for cooking apparatuses on its cookingplate.

Also the present invention can provide a range with oven produced byusing the composite material for cooking apparatuses on its glass door.

Also the present invention can provide a heating pot produced by usingthe composite material for cooking apparatuses.

Also the present invention can provide a heating pot produced byapplying the composite material for cooking apparatuses to its heatingsurface made of metal.

Also the present invention can provide a heating pan produced byapplying the composite material for cooking apparatuses to its glasslid.

Also the present invention can provide a frying pan produced by usingthe composite material for cooking apparatuses.

Also the present invention can provide a frying pan produced by applyingthe composite material for cooking apparatuses to its heating surfacemade of metal.

Also the present invention can provide a fryer produced by using thecomposite material for cooking apparatuses.

Also the present invention can provide a fryer produced by applying thecomposite material for cooking apparatuses to its inner surface made ofmetal.

Also the present invention can provide a fryer produced by applying thecomposite material for cooking apparatuses to its inner surface made ofglass.

Also the present invention can provide a rice cooker produced by usingthe composite material for cooking apparatuses.

Also the present invention can provide a rice cooker produced byapplying the composite material for cooking apparatuses to its innersurface made of metal.

Also the present invention can provide a rice cooker produced byapplying the composite material for cooking apparatuses to its inner lidmade of metal.

Also the present invention can provide a pot produced by using thecomposite material for cooking apparatuses.

Also the present invention can provide a pot produced by applying thecomposite material for cooking apparatuses to its inner surface made ofmetal.

Also the present invention can provide a pot produced by applying thecomposite material for cooking apparatuses to its inner lid made ofmetal.

Also the present invention can provide a tableware or vessel produced byusing the composite material for cooking apparatuses.

Also the present invention can provide a metallic tableware or vesselproduced by using the composite material for cooking apparatuses.

Also the present invention can provide a glass tableware or vesselproduced by using the composite material for cooking apparatuses.

Also the present invention can provide a cooking apparatus forprocessing foods which is produced by using the composite material forcooking apparatuses.

Also the present invention can provide a cooking apparatus for mixingfoods which is produced by using the composite material for cookingapparatuses.

Also the present invention can provide a cooking apparatus for cuttingfoods which is produced by using the composite material for cookingapparatuses.

Also the present invention can provide a bakery apparatus produced byusing the composite material for cooking apparatuses.

In principle the above-mentioned descriptions regarding the coatingcomposition, coating film and methods for production thereof are appliedto the composite material for cooking apparatuses of the presentinvention. Explained below are particularly preferable embodimentsthereof.

Examples of the above-mentioned substrate used usually for the compositematerial for cooking apparatuses of the present invention as a metallicsubstrate are, for instance,

{circle around (1)} cold rolled steel sheet,

{circle around (2)} plated steel sheet, for example, Zn-plated steelsheet, Zn alloy-plated steel sheet, Al-plated steel sheet, Alalloy-plated steel sheet, Cr-plated steel sheet (TFS), Ni-plated steelsheet, Cu-plated steel sheet, galvanized steel sheet, etc.,

{circle around (3)} aluminum sheet,

{circle around (4)} titanium sheet,

{circle around (5)} stainless steel sheet, and the like.

In addition, where transparency is required, a ceramic substrate ofglass and a resin substrate of acrylic resin and polycarbonate areusually used.

A thickness of the metal oxide coating film of the composite materialfor cooking apparatuses of the present invention varies depending onkind and portion of cooking apparatuses to which the film is applied.The thickness is from 0.01 to 100 μm, preferably from 0.01 to 50 μm,particularly preferably from 0.02 to 20 μm.

Cooking apparatuses and parts thereof to which the composite materialfor cooking apparatuses of the present invention is applied areclassified by fields they belong to, and exemplified below. Accordinglythe present invention also relates to cooking apparatuses and partsthereof mentioned below.

Also these classified cooking apparatuses and parts thereof are shown inTables 1 to 7.

{circle around (1)} Pots and pans

(a) Inner surface, inner lid, etc. of electric pot including electricwater heater

In these applications, stain-proofing property (for fur), hot waterresistance and anti-bacterial property of the composite material forcooking apparatuses of the present invention can be used particularlyeffectively.

(b) Inner surface of inner pot, inner lid, etc. of gas and electric ricecookers and rice cookers with rice washing mechanism, etc.

In these applications, non-sticking property (for rice and scorching),stain-proofing property and heat resistance of the composite materialfor cooking apparatuses of the present invention can be usedparticularly effectively. Further it is possible to inhibit lowering ofthe characteristics due to abrasion, scratch, etc. of the coating filmby cleaning with brush, etc.

{circle around (2)} Cooking apparatuses

(a) Surfaces of frying pan, vat, household hand mixer for cooking,crate, kitchen knife, molder for bread, reverse sheet for bread, doughdividing and rounding machine for bread, etc., inner surface of mixingbowl, rice chest, etc. and blade of the above-mentioned mixer

In these applications, non-sticking property (scorching and coheringstains), stain-proofing property and heat resistance of the compositematerial for cooking apparatuses of the present invention can be usedparticularly effectively. Further it is possible to inhibit lowering ofthe characteristics due to abrasion, scratch, etc. of the coating filmby metal spatula, etc.

(b) Inner surface, blade, etc. of electric food processors such aselectric food crusher for domestic use, electric food crusher, electricmeat grinder for kitchen use, electric blender for kitchen use andelectric mixer for kitchen use

In these applications, non-sticking property (for vegetable and meatjuice) and stain-proofing property of the composite material for cookingapparatuses of the present invention can be used particularlyeffectively.

{circle around (3)} Gas oven with grill

(a) Top panel, side panel, surface of gas ranges such as gas containerbuilt-in type oven, and drip pan cover thereof, etc.

In these applications, non-sticking property (for oil stains), heatresistance and transparency (property for exhibiting clear color andpattern) of the composite material for cooking apparatuses of thepresent invention can be used particularly effectively. Further it ispossible to inhibit lowering of the characteristics due to abrasion,scratch, etc. of the coating film by cleaning with brush, etc.

{circle around (4)} Ranges with oven including toaster, range, etc.

(a) Inner surfaces (metallic portion) of ovens (range for kitchen) suchas oven for shop use, electric oven (including oven for shop use),electric oven with heating cabinet for shop use, cooking oven for shopuse and cooking range for shop use; ovens for making bread such asbaking oven for shop use and automatic baking apparatus for domesticuse; electric oven and toaster such as toaster and toaster for bread;and microwave range such as microwave range for shop use and microwaverange with oven; and pans for ranges

In these applications, non-sticking property (for oil and scorching),stain-proofing property and heat resistance of the composite materialfor cooking apparatuses of the present invention can be usedparticularly effectively. Further it is possible to inhibit abrasion andscratch of the coating film by spatula, brush, etc.

(b) Inner surface of door of ranges with oven raised in above (a)

In these applications, non-sticking property, heat resistance andtransparency of the composite material for cooking apparatuses of thepresent invention can be used particularly effectively. In case ofmicrowave range, energy ray resistance can be used particularlyeffectively.

{circle around (5)} Pots and pans

(a) Inner surface of pots and pans such as glass pot, enamel pot,aluminum pot, electric frying pot, electric Tempura pot, electricpressure pot and electric pressure pot for stew, etc.

In these applications, non-sticking property for scorching, coheringstains and oil in case of the frying pot and Tempura pot) and heatresistance of the composite material for cooking apparatuses of thepresent invention can be used particularly effectively. Further it ispossible to inhibit abrasion and scratch of the coating film by spatula,brush, etc.

(b) Lid, etc. of pots and pans raised in above (a)

In these applications, not only the characteristics in above (a) butalso transparency of the composite material for cooking apparatuses ofthe present invention can be used particularly effectively.

{circle around (6)} Garbage disposer

Inner surface, etc. of garbage disposer for domestic use and garbage(waste) disposer for making compost

In these applications, non-sticking property and stain-proofing propertyof the composite material for cooking apparatuses of the presentinvention can be used particularly effectively.

{circle around (7)} Other heating apparatuses for cooking

(a) Heating surface, lid, etc. of griddle

In these applications, non-sticking property (for scorching and coheringstains) and heat resistance of the composite material for cookingapparatuses of the present invention and transparency thereof in case ofthe lid can be used particularly effectively. Further it is possible toinhibit lowering of the characteristics and appearance due to abrasionand scratch of the coating film by metal spatula, etc.

(b) Cooking surface, etc. of electromagnetic cooking apparatuses such aselectromagnetic range and oven

In these applications, non-sticking property, heat resistance andtransparency of the composite material for cooking apparatuses of thepresent invention can be used particularly effectively, and it ispossible to inhibit abrasion and scratch of the coating film by brush,etc.

(c) Inner surface, door inner surface, lid, etc. of electric steamersuch as food steamer for shop use

In these applications, non-sticking property, stain-proofing property,heat resistance and steam resistance of the composite material forcooking apparatuses of the present invention can be used particularlyeffectively, and it is possible to inhibit abrasion and scratch of thecoating film by brush, etc.

(d) Inner surface, lid, etc. of noodle boiler for shop use

In these applications, non-sticking property, stain-proofing property,heat resistance and hot water resistance of the composite material forcooking apparatuses of the present invention can be used particularlyeffectively, and it is possible to inhibit abrasion and scratch of thecoating film by brush, etc.

(e) Inner surface, inner surface (metallic portion) and door innersurface of cooking roaster for shop use, pan for range, etc.

In these applications, non-sticking property (for scorching and coheringstains) and heat resistance of the composite material for cookingapparatuses of the present invention can be used particularlyeffectively, and it is possible to inhibit abrasion and scratch of thecoating film by brush, etc.

(f) Inner surface, etc. of tableware and can washer for shop use

In these applications, non-sticking property, stain-proofing propertyand hot water resistance of the composite material for cookingapparatuses of the present invention can be used particularlyeffectively.

(g) Inner surface, door inner surface, etc. of heating cabinet for shopuse

In these applications, non-sticking property, stain-proofing property,transparency and heat resistance of the composite material for cookingapparatuses of the present invention can be used particularlyeffectively.

Further as the cooking apparatuses other than those mentioned above, towhich the composite material for cooking apparatuses of the presentinvention can be preferably applied, there can be exemplified the samecooking apparatuses as raised in Embodiment 1.

TABLE 1 Classification of Typical finished product productCharacteristics needed Defects of prior art Effect of the invention PotsElectric pot Stain-proofing property Primer is necessary. Adhesiveproperty processability for fur, Processability is not good and (noprimer required), hot water resistance, surface pattern is unclear.abrasion resistance, antibacterial property Abrasion and scratchingoccur scratch resistance, hardness easily. (insufficient durability)Electric rice Non-sticking property for Primer is necessary. Adhesiveproperty processability cooker scorched face, Processability is not goodand (no primer required), heat resistance surface pattern is unclear.abrasion resistance, Abrasion and scratching occur scratch resistance,easily. (insufficient durability) hardness Cooking Frying panNon-sticking property for Processability and transparency Adhesiveproperty, appliances scorch and cohered stain, are not good and surfaceprocessability (no primer required), and utensils stain-proofingproperty, pattern is unclear. Abrasion transparency, heat resistance andscratching occur easily clearer surface pattern, (insufficientdurability) abrasion resistance, scratch resistance, hardness Electricfood Non-sticking property for Processability and transparency Adhesiveproperty, processor vegetable and juice of meat, are not good andsurface improvement of processability stain-proofing property pattern isunclear. (no primer required), transparency, clearer surface patternOven with grill Gas oven Non-sticking property for Processability is notgood and Adhesive property, (toaster, range) stained oil, surfacepattern is unclear. processability (no primer required), heat resistanceScratching occurs easily. transparency, transparency, clear surface(lowering of appearance). clear surface pattern, (color, pattern)abrasion resistance, scratch resistance, hardness Range with oven OvenNon-sticking property for oil Processability, heat resistance Adhesiveproperty (toaster, range) (kitchen range) and scorch, stain-proofing anddurability are not good. (processability), property, heat resistance,Wipe-off property is not good non-sticking property, (No articlestreated with clear surface pattern, transparency fluorine-containingresin are transparency, available). Transparency is not abrasionresistance, good. Abrasion and scratching scratch resistance, hardnessoccur easily. (insufficient durability) Oven for baking breadNon-sticking property for oil Processability, heat resistance Adhesiveproperty and scorch, stain-proofing and durability are not good.(processability), property, heat resistance, Wipe-off property is notgood clear surface pattern, non-sticking property, (No articles treatedwith transparency fluorine-containing resin are transparency,available). Transparency is not abrasion resistance, good. Abrasion andscratching scratch resistance, hardness occur easily. (insufficientdurability) Electric oven and toaster Non-sticking property for oilProcessability, heat resistance Adhesive property and scorch, anddurability are not good. (processability), stain-proofing property,Wipe-off property is not good (clear surface pattern, heat resistance,(No articles are not treated with non-sticking property,fluorine-containing resin are transparency, transparency available).Transparency is not abrasion resistance, good. Abrasion and scratchingscratch resistance, hardness occur easily. (insufficient durability)Microwave oven Non-sticking property, Processability, heat resistanceAdhesive property heat resistance, and durability are not good.(processability), heat resistance to energy ray, Wipe-off property isnot good resistance, durability, transparency fluorine-containing resinare not maintenance of available). Transparency transparency, good.Abrasion and scratching abrasion resistance, occur easily. scratchresistance, (insufficient durability) hardness

TABLE 2 Classification of product Typical finished productCharacteristics needed Defects of prior art Effect of the invention Potand pan Glass pot Non-sticking property for Wipe-off property is notgood Adhesive property scorch and cohering stains, (No articles treatedwith (processability), heat resistance, fluorine-containing resin aretransparency, transparency available). Heat resistance and abrasionresistance, transparency are not good. scratch resistance Abrasion andscratching occur easily. (insufficient durability) Electric deep fryerNon-sticking property for Processability, heat resistance Adhesiveproperty, heat resistance, and wipe-off property are not processability(no primer oil, good (No articles treated with required), transparency,transparency fluorine-containing resin are abrasion resistance,available). Surface pattern is scratch resistance unclear. Transparencyis not good. Abrasion and scratching occur easily (insufficientdurability). Electric pressure cooker Non-sticking property forProcessability, heat resistance Adhesive property, scorching andcohering and wipe-off property are not processability (no primer stains,heat resistance, good (No articles treated with required), transparency,transparency fluorine-containing resin are abrasion resistance,available). Surface pattern is scratch resistance unclear. Transparencyis not good. Abrasion and scratching occur easily (insufficientdurability). Electric pressure pot Non-sticking property forProcessability, heat resistance Adhesive property, for stew scorchingand cohering and wipe-off property are not processability (no primerstains, heat resistance, good (No articles treated with required),transparency, transparency fluorine-containing resin are abrasionresistance, available). Surface pattern is scratch resistance unclear.Transparency is not good. Abrasion and scratching occur easily(insufficient durability).

TABLE 3 Classification of product Typical finished productCharacteristics needed Defects of prior art Effect of the inventionOther heating Griddle Non-sticking property for Processability and heatAdhesive property, appliances scorch and cohering stains, resistance arenot good. processability (no primer for cooking heat resistance,Abrasion and scratching required), heat non-sticking property,(durability) occur easily. resistance, scratch transparency Wipe-offproperty is not good resistance, (No articles treated with transparency,hardness fluorine-containing resin are available). Transparency is notgood. Electromagnetic Non-sticking property, Processability is not good.Adhesive property, cooking appliance heat resistance, Abrasion andscratching processability (no primer transparency occur easily(durability). required), transparency, abrasion resistance, scratchresistance, hardness Electric cooking steamer Non-sticking property,Processability is not good. Adhesive property, stain-proofing property,Abrasion and scratching processability (no primer heat resistance, occureasily (durability). required), abrasion steam resistance resistance,scratch resistance, hardness Noodles boiling Non-sticking property,Processability is not good. Adhesive property, apparatus for shop usestain-proofing property, Abrasion and scratching processability (noprimer heat resistance, occur easily (durability). required), hot waterresistance abrasion resistance, scratch resistance, hardness Otherheating Cooking roaster for Non-sticking property for Processability andheat resistance Adhesive property, appliances shop use scorch andcohering stains, are not good. processability (no primer for cookingheat resistance Abrasion and scratching occur required), transparency,easily (durability). abrasion resistance, scratch resistance, hardnessTablewares and cans Non-sticking property, Processability is not good.Adhesive property, washing machine for stain-proofing property, Surfacepattern is unclear. processability (no primer shop use hot waterresistance required) Heat cabinet for Non-sticking property,Processability and transparency Adhesive property, shop usestain-proofing property, are not good. processability (no primertransparency, Surface pattern is unclear. required) heat resistanceGarbage Garbage disposer Non-sticking property, Processability is notgood. Adhesive property, disposer stain-proofing property Surfacepattern is unclear. processability (no primer required)

TABLE 4 Classification Typical finished of product product Similarproduct Application Pots Electric pot Inner surface, inner lid Electricwater heater Inner surface, inner lid Electric rice cooker Inner surfaceof inner pot, inner lid Rice cooker (gas, electric) Inner surface ofinner pot, inner lid Rice cooker (with rice washing Inner surface ofinner pot, inner lid mechanism for shop use) Cooking Frying pan Surfaceappliances Vat Surface and utensils Mixing bowl Inner surface Choppingboard Surface Household hand-operated mixer for Surface, blade cookingCrate Surface Cooking knife Surface Mold for making bread SurfaceReverse sheet for making bread Surface Dough dividing and roundingSurface machine for making bread Rice chest primer surface Electric foodprocessor Inner surface, blade Household electric food crusher Innersurface Blade Electric food crusher Inner surface Blade Electric meatgrinder for kitchen use Inner surface Blade Electric blender for kitchenuse Inner surface Blade Electric mixer for kitchen use Inner surfaceBlade Preferred Example of substrate polymer* Metal oxide Applyingmethod Other similar product Metal (aluminum, I, II Si, Al, Ti Coatinggalvanized steel plate) Metal (aluminium, Rice gruel cooker, galvanizedsteel plate) rice warmer Metal I, II Si, Al, Ti Coating Metal MetalCooking utensils SUS, aluminum Cooking utensils (for slicing) SUS,aluminum Cooking utensils Resin, wood Cooking appliances and utensilsSUS, resin Cooking appliances (food) SUS, resin I, II, III Si, Al, TiCoating Electric cooking appliances SUS Cooking iron SUS Cookingappliances and facilities Metal Barbecue utensils Metal Food processingmachine and Metal utensils (with press machine) Metal Cooking appliancesfor mixing, Metal vegetable slicer, food slicer, Metal peeler, cutterfor cutting into Metal, glass small cubes, food cutter, meat Metalchopper, meat slicer, meat Metal, glass I, II, III Si, Al, Ti Coatingtenderizer, cutter mixer, mixer, food Metal mixer, blender, appleprocessor, Metal, glass continuous egg opening machine, Metal soy beancurd cutter, food molder, Metal, glass bread crumb coating machine,Metal vegetable washing machine *Fluorine-containing ethylenic polymer(A) having functional group of the present invention

TABLE 5 Classification Typical finished of product product Similarproduct Application Gas oven with Gas oven Top plate, side plate, outersurface grill Gas container built-in type gas oven Top plate, sideplate, outer surface Hood for drip pan of gas oven Outer surface (madeof metal) Range with oven Oven (kitchen range) Inner surface (metallicportion), pan for range, (toaster, range) Inner surface of door Oven forshop use Inner surface (metallic portion), pan for range, Inner surfaceof door Electric oven Inner surface (metallic portion), pan for range,Inner surface of door Electric oven Inner surface (metallic portion),pan for range, (with heating cabinet for shop use) Inner surface of doorElectric oven (for shop use) Inner surface (metallic portion), pan forrange, Inner surface of door Oven for shop use Inner surface (metallicportion), pan for range, Inner surface of door Cooking oven for shop useInner surface (metallic portion), pan for range, Inner surface of doorCooking range for shop use Inner surface (metallic portion), pan forrange, Inner surface of door Oven for baking bread Inner surface(metallic portion), pan for range, Inner surface of door Oven for bakingbread for shop use Inner surface (metallic portion), pan for range,Inner surface of door Bread baker Inner surface (metallic portion), panfor range, (automatic, for domestic use) Inner surface of door Exampleof substrate Preferred polymer* Metal oxide Applying method Othersimilar product Metal Portable range, oven with grill, Metal I, II Si,Al, Ti Coating portable electric range, Metal electric oven with grillgas range, gas oven with grill Metal Gas salamander, Metal, glasselectric salamander, Metal convection Metal, glass oven Metal Metal,glass Metal Metal, glass Metal I, II Si, Al, Ti Coating Metal, glassMetal Metal, glass Metal Metal, glass Metal Metal, glass Metal Oven forbaking bread Metal, glass Metal Metal, glass I, 11 Si, Al, Ti CoatingMetal Metal, glass *Fluorine-containing ethylenic polymer (A) havingfunctional group of the present invention

TABLE 6 Classification Typical finished of product product Similarproduct Application Range with oven Electric oven and Inner surface(metallic portion), pan for range, (toaster, range) toaster Innersurface of door Toaster Inner surface (metallic portion), pan for range,Inner surface of door Toaster for bread Inner surface (metallicportion), pan for range, Inner surface of door Microwave oven Innersurface (metallic portion), pan for range, Inner surface of doorMicrowave range for shop use Inner surface (metallic portion), pan forrange, Inner surface of door Microwave range with oven Inner surface(metallic portion), pan for range, Inner surface of door Rice cookerInner surface (for microwave range) Pan and pot Glass pot Inner surface,lid Enamel pot Inner surface, lid Aluminum pot Inner surface, lidElectric frying pot Inner surface of pot, lid Inner surface of pot, lidElectric Tempura frying pot Inner surface of pot, lid Inner surface ofpot, lid Electric pressure Inner surface of pot, lid cooker Innersurface of pot, lid Electric pressure pot Inner surface of pot, lid forstew Inner surface of pot, lid Example of substrate Preferred polymer*Metal oxide Applying method Other similar product Metal Metal, glassMetal Metal, glass I, II Si, Al, Ti Coating Metal Metal, glass MetalMetal, glass Metal Metal, glass I, II Si, Al, Ti Coating Metal Metal,glass Metal Glass Wok set for Chinese dishes, one-handed pot,double-handed pot Metal I, II Si, Al, Ti Coating Gas fryer,electromagnetic fryer, Glass Tempura fryer, oil filter unit Metal GlassMetal Buckwheat boiling pot, I, II Si, Al, Ti Coating Glass rotary potMetal I, II Si, Al, Ti Coating Glass *Fluorine-containing ethylenicpolymer (A) having functional group of the present invention

TABLE 7 Classification Typical finished of product product Similarproduct Application Other heating Griddle Heating surface appliance Lidfor cooking Electromagnetic cooking Cooking surface applianceElectromagnetic range and oven Cooking surface Electric cooking steamerInner surface Inner surface of door Food steamer for shop use Innersurface Lid Noodle boiling apparatus Inner surface for shop use LidCooking roaster for Inner surface  Inner surface of door shop useCooking roaster for shop use Inner surface (metallic portion), pan forrange Tablewares and cans washing machine for Inner surface shop useHeating cabinet for Inner surface   Inner surface of door shop useGarbage disposer Garbage disposer Inner surface Garbage disposer(wastes), garbage Inner surface disposer for household use, Innersurface garbage disposer for making compost Inner surface Example ofsubstrate Preferred polymer* Metal oxide Applying method Other similarproduct Metal Electric cooking griddle for fried Metal, glass I, II Si,Al, Ti Coating dumpling stuffed with minced pork Metal Electromagneticrange I, II Si, Al, Ti Coating Metal Metal Gas cooking steamer, MetalElectric cooking steamer Metal I, II Si, Al, Ti Coating Metal, glassMetal I, II Si, Al, Ti Coating Metal, glass Metal, glass I, II Si, Al,Ti Coating Metal Metal } I, II, III } Si, Al, Ti } Coating Thawing box,food warmer, soup kettle, coffee maker, tea server, Metal, glass I, II,III Si, Al, Ti Coating juice dispenser, miso soup dispenser, Sake warmerMetal Metal Metal I, II, III Si, Al, Ti Coating Metal, glass*Fluorine-containing ethylenic polymer (A) having functional group ofthe present invention

EMBODIMENT 7 (Composite Material for Building)

With respect to building materials such as building glass, variousinterior and exterior wall materials, roofing materials and interior andexterior materials and construction materials such as sign, signal,guardrail, utility pole and sound-proof wall, since they are usedexposed to environment, the surfaces thereof are required to haveweather resistance, stain-proofing property against dust, exhaust gasand rain water, transparency and property for exhibiting clear surfacepattern. Also various furnitures, kitchen apparatuses such as gas ovenwith grill and range hood, and housing facilities such as coordinatedkitchen units, washstand, lavatory and bath room are required to haveheat resistance, and non-sticking property and stain-proofing propertyagainst oil, scorch and fur. In Embodiment 7, all the above-mentionedproducts are referred to as “building materials”. These buildingmaterials are made of glass, metal, ceramic, synthetic resin orconcrete. Some of them are not subjected to any treatment on theirsurfaces, but to meet the mentioned requirements, on composite materialsused for these building materials is applied a fluorine-containingpolymer having heat resistance, chemical resistance, corrosionresistance, weather resistance, surface characteristics (non-stickingproperty, low friction property, etc.), electric insulating property,etc. However since the fluorine-containing polymer has not enoughadhesion to a surface of substrate such as metal due to its excellentnon-sticking property, it is necessary to (1) use an adhesive or (2)carry out sand-blasting or etching by electrochemical method to make asurface of the substrate rough for adhering by anchor.

However it is not possible to make the best use of transparency of aglass substrate and color tone such as metal gloss of a metallicsubstrate and thus there is a problem with property for exhibiting clearsurface pattern, since in the method using an adhesive like the method(1), no transparent adhesive having heat resistance and high adhesivityis available, and also since in the method for making the substratesurface rough like the method (2), the substrate surface is made roughsignificantly. Further even if a transparent adhesive is developed,since a fluorine-containing polymer composing a coating film on asurface of a building material, etc. is soft, for example, due to longterm use or by cleaning with a brush, the coating film is injured andthus transparency is lowered and a surface pattern of a substratebecomes unclear, or for example, due to abrasion, inherent weatherresistance, stain-proofing property, water-repellency and non-stickingproperty of a fluorine-containing polymer are lowered. Further since thepolymer is soft, when it is used on exterior building material, foreignmatter, dusts, stains, etc. easily enter into a coating film and thecoating film is easily stained, and thus there is a case where stainsare hardly removed.

To solve them, there have been made trials to endow the coating filmcomprising the fluorine-containing polymer with hardness by adding aglassy or aluminum-based inorganic filler. However there were problemsthat the coating film became fragile, transparency was lowered and asurface pattern of a substrate became unclear.

Also there have been made various studies to endow glass withwater-repellency for the purpose of repelling rain water on a windowglass and fender mirror of cars in rainy days and making field of viewclear. It can be considered that the results of such studies are used inthe field of building materials.

To cope with these problems, the proposals have been made (inJP-A-4-124047, JP-A-4-325446, JP-A-5-24885, JP-A-4-359086,JP-A-5-170486, JP-A-5-213633, JP-A-5-51238, JP-A-6-329442,JP-A-6-340451, JP-A-7-102207, JP-A-7-157335).

However as mentioned above, even by these conventional sol-gel methods,coating films which are suitable for a composite material for buildingmaterial and have, in addition to adhesive property and transparency,excellent abrasion resistance, heat resistance, water- andoil-repellency and scratch resistance have not been obtained.

The composite material for building which is obtained by applying thecoating composition of the present invention to the substrate can beused on various building materials including building glass, buildingmember, kitchen facilities and apparatuses, housing facilities andappliances and various members in the field of construction firstlybecause fine particles of the fluorine-containing ethylenic polymer (A)having functional group are dispersed uniformly in the coating filmcomprising the metal oxide (B) because of their good interfacialadhesivity and the coating film has enough hardness, transparency andadhesive property, and secondly because the coating film comprising thefluorine-containing ethylenic polymer (A) having functional group andthe metal oxide (B) has good weather resistance, stain-proofingproperty, non-sticking property, water-repellency, heat resistance,abrasion resistance and scratch resistance.

The present invention can provide the composite material for buildingcomprising a substrate and, on a surface of the substrate, a coatingfilm which comprises the metal oxide (B) and the fine particles of thefluorine-containing ethylenic polymer (A) having functional groupprepared by copolymerizing:

(a) 0.05 to 50% by mole of at least one of fluorine-containing ethylenicmonomer having at least one functional group selected from the groupconsisting of hydroxyl, carboxyl, a carboxylic salt group, a carboxylicester group and epoxy, and

(b) 50 to 99.95% by mole of at least one of fluorine-containingethylenic monomers having no functional group mentioned above; the fineparticles of the polymer (A) are contained in dispersed state in themetal oxide (B) layer.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned fluorine-containing ethylenicmonomer (a) having functional group is at least one offluorine-containing ethylenic monomers having functional group andrepresented by the formula (1):

CX₂═CX¹—R_(f)—Y   (1)

wherein Y is —CH₂OH, —COOH, a carboxylic salt group, a carboxylic estergroup or epoxy, X and X¹ are the same or different and each is hydrogenatom or fluorine atom, R_(f) is a divalent fluorine-containing alkylenegroup having 1 to 40 carbon atoms, a fluorine-containing oxyalkylenegroup having 1 to 40 carbon atoms, a fluorine-containing alkylene grouphaving ether group and 1 to 40 carbon atoms or a fluorine-containingoxyalkylene group having ether bond and 1 to 40 carbon atoms.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned fluorine-containing polymer (A )having functional group is the polymer (I).

Also the present invention can provide the composite material forbuilding, in which the above-mentioned fluorine-containing polymer (A)having functional group is the polymer (II).

Also the present invention can provide the composite material forbuilding, in which the above-mentioned fluorine-containing polymer (A)having functional group is the polymer (III).

Also the present invention can provide the composite material forbuilding, in which the above-mentioned metal oxide (B) is a siliconoxide.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned metal oxide (B) is an aluminumoxide.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned metal oxide (B) is a titaniumoxide.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned substrate is a metallicsubstrate.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned substrate is a synthetic resinsubstrate.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned synthetic resin substrate istransparent.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned synthetic resin substrate is apolycarbonate substrate.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned synthetic resin substrate is anartificial marble substrate.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned substrate is a non-metallicinorganic substrate.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned non-metallic inorganic substrateis a glass substrate.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned non-metallic inorganic substrateis a concrete substrate.

Also the present invention can provide the composite material forbuilding, in which the above-mentioned non-metallic inorganic substrateis a cement substrate.

Also the present invention can provide an exterior member for buildingproduced by using the composite material for building.

Also the present invention can provide a curtain wall produced by usingthe composite material for building.

Also the present invention can provide a roofing member produced byusing the composite material for building.

Also the present invention can provide a roofing tile produced by usingthe composite material for building.

Also the present invention can provide a roofing material produced byusing the composite material for building.

Also the present invention can provide a window member produced by usingthe composite material for building.

Also the present invention can provide sashes produced by using thecomposite material for building.

Also the present invention can provide a rain trough produced by usingthe composite material for building.

Also the present invention can provide exteriors produced by using thecomposite material for building.

Also the present invention can provide a door produced by using thecomposite material for building.

Also the present invention can provide an outdoor fence produced byusing the composite material for building.

Also the present invention can provide an interior member for buildingproduced by using the composite material for building.

Also the present invention can provide a wall material produced by usingthe composite material for building.

Also the present invention can provide a flooring material produced byusing the composite material for building.

Also the present invention can provide a ceiling produced by using thecomposite material for building.

Also the present invention can provide a material for fixtures producedby using the composite material for building.

Also the present invention can provide an interior door produced byusing the composite material for building.

Also the present invention can provide a blind produced by using thecomposite material for building.

Also the present invention can provide housing facilities andapparatuses produced by using the composite material for building.

Also the present invention can provide bath and toilet utensils producedby using the composite material for building.

Also the present invention can provide a washstand produced by using thecomposite material for building.

Also the present invention can provide a toilet bowl produced by usingthe composite material for building.

Also the present invention can provide a bath tub produced by using thecomposite material for building.

Also the present invention can provide a member for kitchen produced byusing the composite material for building.

Also the present invention can provide coordinated kitchen unitsproduced by using the composite material for building.

Also the present invention can provide a gas oven with grill produced byusing the composite material for building.

Also the present invention can provide a range hood produced by usingthe composite material for building.

Also the present invention can provide an elevator produced by using thecomposite material for building.

Also the present invention can provide an escalator produced by usingthe composite material for building.

Also the present invention can provide a building material forconstruction produced by using the composite material for building.

Also the present invention can provide a member for constructing a roadproduced by using the composite material for building.

Also the present invention can provide a sound-proof wall forconstruction of a road produced by using the composite material forbuilding.

Also the present invention can provide a sign for construction of a roadproduced by using the composite material for building.

Also the present invention can provide a guard-rail for construction ofa road produced by using the composite material for building.

Also the present invention can provide a signal cover for constructionof a road produced by using the composite material for building.

Also the present invention can provide an electric lamp cover forconstruction of a road produced by using the composite material forbuilding.

Also the present invention can provide water supply and drainage membersproduced by using the composite material for building.

Also the present invention can provide members for bridge produced byusing the composite material for building.

Also the present invention can provide a member for railway constructionproduced by using the composite material for building.

Also the present invention can provide a bolt for railway constructionproduced by using the composite material for building.

Also the present invention can provide a signal cover for railwayconstruction produced by using the composite material for building.

Also the present invention can provide a wiring for railway constructionproduced by using the composite material for building.

Also the present invention can provide a steel tower for railwayconstruction produced by using the composite material for building.

Also the present invention can provide members for power supply plantproduced by using the composite material for building.

Also the present invention can provide a glass for power supply plantproduced by using the composite material for building.

Also the present invention can provide a utility pole for power supplyplant produced by using the composite material for building.

Also the present invention can provide an arm for power supply plantproduced by using the composite material for building.

Also the present invention can provide a member for chemical plantproduced by using the composite material for building.

In principle the above-mentioned descriptions regarding the coatingcomposition, coating film and methods for production thereof are appliedto the composite material for building of the present invention.Explained below are particularly preferable embodiments thereof.

Examples of the substrate usually used for the composite material forbuilding of the present invention are metallic plates of aluminum,stainless steel, iron and titanium; metallic plates subjected to hot-dipzinc coating, aluminum plating, etc.; metallic plates subjected tochemical conversion treatment such as oxidation with chromic acid,phosphoric acid, etc.; alumite-treated metallic plates subjected toanodizing; and the like.

Examples of the non-metallic inorganic substrate used usually are glasssubstrates such as crystallized glass, foam glass, heat reflectingglass, heat absorbing glass and composite glass; ceramic substrates suchas tile, large size pottery plate, ceramic panel and brick; naturalstones such as granite and marble; concrete substrates such as highstrength concrete, glass fiber-reinforced concrete (GRC), carbonfiber-reinforced concrete (CFRC), lightweight aerated concrete (ALC) andcomposite ALC; cement substrates such as extrusion molded cement andcomposite molded cement; asbestos slate; enamelled steel plate; and thelike.

Further examples of the synthetic resin substrate used arepolycarbonate, polyester resin, acrylic resin, vinyl chloride resin,artificial marble (mainly comprising unsaturated polyester resin oracrylic resin), steel plates coated with vinyl chloride resin, acrylicresin or urethane resin, and the like.

Among them, where transparency is required, the non-metallic inorganicsubstrate of glass and the synthetic resin substrate of acrylic resinand polycarbonate are usually used.

The substrates used in the present invention may be in the form ofsheet, film, tube, pipe, plate or bar or in other irregular form.However it is preferable that the form is the same as or similar to thatof a finished product from the viewpoint of processability.

A thickness of the metal oxide coating film of the above-mentionedcomposite material for building of the present invention variesdepending on kind and portion of building materials to which the film isapplied. The thickness is from 0.01 to 100 μm, preferably from 0.1 to 70μm, particularly preferably from 1 to 50 μm.

Building materials and parts thereof which can employ the compositematerial for building of the present invention are classified by thefields thereof and exemplified below. Accordingly the present inventionrelates to the building materials and various parts thereof mentionedbelow.

Those building materials and parts thereof are itemized, classified andshown in Tables 8 to 17. Those mentioned in the column “Metal oxide” arepreferable metals (M) composing the metal oxide (B).

{circle around (1)} Glass for building

Building glass, polished flat glass for building (window glass), windowof stained glass, windshield glass, light shielding ratio adjustableglass, etc.

In these applications, transparency, stain-proofing property and flameretardancy of the composite material for building of the presentinvention can be used particularly effectively.

{circle around (2)} Outer wall material, roofing material and interiorand exterior material (made of metal)

(a) Exterior metallic building material for wall, metallic buildingmaterial, interior and exterior metal panel for building, metal fence,metallic tile, metallic building panel, etc.

(b) Metallic roofing material, solar system built-in roofing material,etc.

(c) Metallic door, metallic grating, metallic shutter, metallic fence,metallic porch (for building), etc.

(d) Metallic blind (for outdoor use), gutter, sash, rain door, etc.

(e) Metallic ceiling panel, metallic floor tile, metallic wall sheetcoated with decorative vinyl chloride sheet, etc.

(f) Metallic parking facilities for cars, metallic object of art, etc.

In these applications, weather resistance, stain-proofing property andtransparency (property for exhibiting clear surface pattern) of thecomposite material for building of the present invention can be usedparticularly effectively.

{circle around (3)} Outer wall material, roofing material and interiorand exterior material (non-metallic inorganic material)

(a) Segmental concrete block or concrete block bonded with a tile orsliced natural stone, segmental concrete road pavement board or concreteroad pavement board having a surface of rubber material, concrete boardwhich may be reinforced with GRC (fiber-reinforced concrete) wallmaterial, etc.

(b) Extrusion-molded cement such as cement having tile-like surface

(c) Building stone such as artificial stone

(d) Building tile, luster-finished tile, floor tile, ceramic tile andborder tile made of pottery

(e) Exterior material for building and for wall such as non-metallicexterior material for building, building material and building panel andwall tile for building

(f) Roofing material such as solar system built-in roofing material madeof ceramic

(g) Gravestone and grave-post

(h) Small sculpture, standing sculpture, image, bust and other object ofart made of stone, concrete or marble

In these applications, weather resistance, stain-proofing property,water-proofing property, transparency (property for exhibiting clearsurface pattern), processability and adhesive property of the compositematerial for building of the present invention, abrasion resistancethereof in case of above (c) and weathering preventing property thereofin cases of (g) and (h) can be used particularly effectively.

{circle around (4)} Outer wall material, roofing material and interiorand exterior material (made of resin)

(a) Floor panel, ceiling panel, etc.

(b) Grating, gutter and blind and door for indoor use, etc.

(c) Plastic panel for concrete

(d) Gasket for building

(e) Curtain, cover and sunshield with an insect-proofing, ultravioletray and heat shielding and scatter preventing film

(f) Flooring material made of stone or flooring material made ofpolyvinyl chloride and having a surface of stone pattern

(g) Solar system built-in plastic roofing material

(h) Sectional polyvinyl chloride tile having clearance and being capableof draining water

(i) Synthetic resin sash

(j) Decorative board for counter, furniture, sill, wall panel,bucksplash, baseboard, wall of bathroom and shower room

(k) Prefabricated assembly set for washstand, shower room, lavatory,transferable toilet, public toilet, etc.

(l) Assembly set of sauna room, garage, etc.

In these applications, weather resistance, stain-proofing property,transparency (property for exhibiting clear surface pattern), waterresistance, processability and adhesive property of the compositematerial for building of the present invention can be used particularlyeffectively.

{circle around (5)} Outer wall material and roofing material (made ofwood)

(a) Timber for household utensils and timber and decorative panel forbuilding such as veneer and wooden panel, etc.

(b) Wooden fence, door and window frame for indoor use, etc.

(c) Wooden panel for building produced by adhering elastic rubbermaterial on the back of plywood

(d) Wooden assembly set for building

In these applications, weather resistance, stain-proofing property,transparency (property for exhibiting clear surface pattern), waterresistance, processability and adhesion of the composite material forbuilding of the present invention can be used particularly effectively.

{circle around (6)} Furniture

(a) Glass showcase, wagon, display wagon, display panel, display stand,meal conveying wagon, flower stand, etc.

(b) Shelf, screen, desk, sofa, shelf for chest of drawers, etc.

(c) Telephone booth made of metal or various materials

In these applications, stain-proofing property, transparency (propertyfor exhibiting clear surface pattern), water resistance andprocessability of the composite material for building of the presentinvention and further property for preventing paper from being pasted,adhesive property, abrasion resistance and scratch resistance thereof incase of above (c) can be used particularly effectively.

{circle around (7)} Apparatuses for household and shop uses

(a) Gas oven with grill, range hood, ventilation hood, etc.

(b) Metallic duct for central heating, ventilator, air conditioner, etc.

In these applications, stain-proofing property, non-sticking property(against oil stains), processability and adhesive property of thecomposite material for building of the present invention can be usedparticularly effectively.

{circle around (8)} Housing facilities and appliances

(a) Coordinated kitchen units including range for kitchen (oven), sink,etc.

(b) Electrically heated, gas heated and oil heated water heaters(including instantaneous water heater)

(c) Wall-mounted washbasin, washstand, hair washing appliance fordomestic use, washstand with hair washing function, washbasin forwashstand, washbasin with cover, bow window type washstand, etc.

(d) Flush toilet stool, small size chamber pot for car, urinal, toiletstool with urinalyzer, toilet stool for little children, toilet stoolwith hot water washing mechanism, toilet seat with deodorizing unit andwater tank for flush toilet

(e) Lining for bathrooms including shower room, sauna bath for domesticand shop uses, bath tubs such as prefabricated bath tub, bath tub withbubble generator and bath utensils such as handle mounted on bath tuband soap holder

(f) Escalator, elevator (including those for private houses), etc.

In these applications, stain-proofing property, property for exhibitingclear surface pattern (transparency) and processability of the compositematerial for building of the present invention, and further heatresistance thereof in cases of above (a), (b) and (e), abrasionresistance and scratch resistance thereof in cases of above (c) to (e)and sliding property and corrosion resistance thereof in case of above(f) can be used particularly effectively.

{circle around (9)} Construction

(a) Sign for bus stop, sign for street, sign mounted on guardrail, etc.

(b) Signals such as luminous signal and mechanical signal

(c) Guardrail produced by using various materials

(d) Utility pole produced by using various materials

(e) Sound-proof wall

(f) Plastic molding frame for forming concrete for building andstructure

In these applications, weather resistance, stain-proofing property,scratch resistance, transparency (property for exhibiting clear surfacepattern), processability and adhesive property of the composite materialfor building of the present invention and further mold-release propertythereof in case of above (f) can be used particularly effectively.

TABLE 8 Classification Sub-classification Typical example of finishedproduct Characteristics needed Defects of prior art Glass Building glassBuilding glass Weather resistance, Occurrence of staining,stain-proofing property insufficient weather (stains due to rain water)resistance (resistance to surface treating agent) Building Outer wallmaterial, Exterior building material made of Weather resistance,insufficient adhesive property material roofing material and metal forwall stain-proofing property (to fluorine-containing resin), interiorand exterior (stains due to rain water) occurrence of staining andrusting material (made of metal) Roofing material made of metal Weatherresistance, insufficient adhesive property stain-proofing property (tofluorine-containing resin), (stains due to rain water) occurrence ofstaining and rusting Metal door Weather resistance, insufficientadhesive property stain-proofing property (to fluorine-containingresin), (stains due to rain water) occurrence of staining and rustingMetal blind Weather resistance, insufficient adhesive propertystain-proofing property (to fluorine-containing resin), (stains due torain water) occurrence of staining and rusting Metal shutter Weatherresistance, insufficient adhesive property stain-proofing property (tofluorine-containing resin), (stains due to rain water) occurrence ofstaining and rusting Metal ceiling panel Weather resistance,Insufficient adhesive property stain-proofing property (tofluorine-containing resin), (transparency) occurrence of staining andrusting Others Weather resistance, insufficient adhesive propertystain-proofing property, (to fluorine-containing resin), clear surfacepattern occurrence of staining and rusting (transparency) Building Outerwall material, Concrete board (with reinforced Weather resistance,Insufficient adhesive property material roofing material and truss)stain-proofing property, (to fluorine-containing resin), exteriormaterial excluding water-proofness occurrence of staining those made ofmetal Cement (extraction molding) Weather resistance, Insufficientadhesive property (inorganic) stain-proofing property, (tofluorine-containing resin), water-proofness Building stone Weatherresistance, Insufficient adhesive property stain proofing property, (tofluorine-containing resin), occurrence of staining, low abrasionresistance Tile (excluding those made of metal) Weather resistance,Insufficient adhesive property stain-proofing property, (tofluorine-containing resin), clear surface pattern occurrence ofstaining, (transparency), poor transparency, abrasion resistance lowabrasion resistance Exterior building material for wall Weatherresistance, Insufficient adhesive property (excluding those made ofmetal) stain-proofing property (to fluorine-containing resin), (stainsdue to rain water), occurrence of staining water proofness Roofingmaterial Weather resistance, Insufficient adhesive property (excludingthose made of metal) stain-proofing property, (to fluorine-containingresin), transparency, occurrence of staining water proofness Grave stoneWeather resistance, Insufficient adhesive property stain-proofingproperty, (to fluorine-containing resin), transparency occurrence ofstaining (clear surface pattern) prevention of weathering Sculpturesmade of stone Weather resistance, Insufficient adhesive propertyconcrete or marble stain-proofing property, (to fluorine-containingresin), transparency (clear surface occurrence of staining pattern),prevention of weathering

TABLE 9 Typical example of Example of Preferred Metal ApplyingClassification Sub-classification finished product substrate polymer*oxide method Effect by polymer* Glass Building glass Building glassGlass I-III Si, Al, Ti Coating Processability (direct adhesion),prevention of scattering, maintenance of transparency Building Outsidewall Exterior building Metal, Processability material material, roofingmaterial made of metal Aluminum (no primer required) material and forwall I, III Si, Al, Ti Coating clear surface pattern, interior andtransparency exterior material Roofing material made of Metal,Processability (made of metal) metal aluminum I-III Si, Al, Ti Coating(no primer required) SUS Metal door Metal, Processability aluminum,I-III Si, Al, Ti Coating (no primer required), steel plate clear surfacepattern Metal blind Metal, Processability aluminum, I-III Si, Al, TiCoating (no primer required), steel plate clear surface pattern Metalshutter Metal, Processability aluminum, I-III Si, Al, Ti Coating (noprimer required), steel plate clear surface pattern Metal ceiling panelMetal, Processability (no primer aluminum I-III Si, Al, Ti Coatingrequired), steel plate clear surface pattern Others Metal I-III Si, Al,Ti Coating Processability (no primer required), clear surface patternBuilding Outside wall Concrete board Ceramic, Processability (no primermaterial material, roofing (with reinforced truss) pottery, required),adhesive material and rubber, property, transparency exterior materialstone, I-III Si, Al, Ti Coating excluding those concrete made of metal(inorganic) Cement Cement I-III Si, Al, Ti Coating Processability (noprimer (extraction molding) required), adhesive property, transparencyBuilding stone Resin I-III Si, Al, Ti Coating Processability (no primerrequired), adhesive property, transparency. Tile (excluding thoseCeramic, Processability (no primer made of metal) pottery required),adhesive I-III Si, Al, Ti coating property, transparency, abrasionresistance Exterior building Concrete, Processability (no primermaterial for wall resin, required), adhesive (excluding those madeceramic I-III Si, Al, Ti Coating property, transparency of metal)pottery, wood Roofing material Ceramic, Processability (excluding thosemade of metal I-III Si, Al, Ti Coating (no primer required), metal)adhesive property Grave stone Stone I-III Si, Al, Ti CoatingProcessability (no primer required), adhesive property, transparencySculptures made of Stone, Processability (no primer stone, concrete orconcrete, I-III Si, Al, Ti Coating required), adhesive marble marbleproperty, transparency *Fluorine-containing ethylenic polymer havingfunctional group of the present invention

TABLE 10 Typical example of Classification Sub-classification finishedproduct Similar applications Applications Glass Building glass Buildingglass Polished flat glass for building Window glass, glass (windowglass), curtain wall for building stained glass for window, windshieldglass, glass with light shield adjusting function Building Outer wallmaterial, Exterior building Metallic building material Structures suchas medium- or material roofing material and material made of Interiorand exterior metal panels for building high-storied buildings andhouses, interior and exterior metal for wall Metal fence aluminumcurtain wall material (made of metal) Metal tile Metal panel forbuilding Roofing material Roofing material (made of metal with aStructures such as houses made of metal built-in solar system) Metaldoor Metal grating Structures such as buildings and Metal shutterlarge-scale building structures, Metal fence exterior Metal porch (forbuilding) Metal blind Metal blind (for outdoor use) Structures such asbuildings and Blind (for outdoor use, made of metal) houses, interior,exterior, car Blind (made of metal) Metal shutter Gutter (made of metal)Structures such as Sash medium-storied buildings and houses, mansionMetal ceiling panel Metal floor tile Structures such as building andWall panel (made of metal, coated with houses decorating vinyl chloridesheet) Others Parking facilities made of metal for cars Metal object ofart Building Outer wall material, Concrete board Concrete block (withtile adhered thereto) Structures such as medium- or material roofingmaterial and (with reinforced Concrete road pavement board high-storiedbuildings and houses, exterior material truss) (having rubber surface)road pavement excluding those Concrete block (with sliced natural stonemade of metal adhered thereto) (inorganic) Concrete road pavement board(segment form) Concrete block (segment form) Wall material made of GRC(fiber-reinforced concrete) Cement Cement Structures such as medium- or(extraction molding) (Having a tile-like surface) high-storied buildingsand houses Building stone Artificial stone Structures such as medium-or - high-storied buildings and houses Tile Building tile (excludingthose made of metal) Structures such as medium- or (excluding those Tile(coated with luster) high-storied buildings and houses, made of metal)Floor tile (excluding those made of metal) floors of bath, swimmingpool, Ceramic tile road pavement, footpath and Border tile made ofpottery stairway Building Outer wall material, Exterior buildingExterior material for building Structures such as medium- or materialroofing material and material for wall (excluding those made of metal)high-storied buildings and houses exterior material (excluding thoseBuilding material excluding those made of metal) (excluding those madeof metal) made of metal Building panel (excluding those made of metal)(inorganic) Wall tile for building (excluding those made of metal)Roofing material Roofing material Structures such as medium- or(excluding those (made of ceramic with built-in solar system)high-storied buildings and houses made of metal) Roofing material (madeof composite building material with built-in solar system) Grave stoneGrave stone Grave-post (excluding those made of metal) Sculptures madeSmall sculpture made of stone, Monument of stone, concrete or marbleconcrete or marble Small standing sculpture made of stone, concrete ormarble Sculpture made of stone, concrete or marble Art work made ofstone, concrete or marble

TABLE 11 Classification Sub-classification Typical example of finishedproduct Characteristics needed Defects of prior art Building Outer wallmaterial, Ceiling panel Stain-proofing property, Insufficient adhesiveproperty material roofing material and (excluding those made of metal)clear surface pattern (to fluorine-containing resin), exterior material(transparency) occurrence of staining (made of resin) Door Weatherresistance, Insufficient adhesive property (excluding those made ofmetal) stain-proofing property (to fluorine-containing resin),occurrence of staining Plastic panel for concrete Weather resistance,Insufficient adhesive property stain-proofing property (tofluorine-containing resin), Gasket for building Weather resistance,Mainly silicon-made gasket stain-proofing property (strength, waterresistance), Sun shield with a film for insect Weather resistance,Occurrence of staining proof ultraviolet ray and heat ray stain-proofingproperty, shielding and glass scatter transparency prevention Floormaterial (made of stone or Weather resistance, Insufficient adhesiveproperty vinyl chloride resin provided with clear surface pattern (tofluorine-containing resin), stone pattern on its surface (transparency)occurrence of staining Roofing material (made of plastic Weatherresistance, Insufficient adhesive property with built-in solar system)stain-proofing property, (to fluorine-containing resin), Tile (ofsectional type having a gap, transparency occurrence of staining beingcapable of draining water and Weather resistance, Insufficient adhesiveproperty made of polyvinyl chloride) stain-proofing property, (tofluorine-containing resin), transparency occurrence of stainingSynthetic resin sash Weather resistance, Insufficient adhesive propertystain-proofing property, (to fluorine-containing resin), transparencyoccurrence of staining Building Outer wall material, Decorative panel(made of Stain-proofing property insufficient adhesive property materialroofing material and thermosetting polymer alloy and clear surfacepattern (to fluorine-containing resin), exterior material used forcounter furniture, door (transparency) occurrence of staining, (made ofresin) sill, wall panel, baseboard for back unclear surface patternsplash, bath room and shower room walls and wainscot) Lavatory assemblyset Weather resistance, Insufficient adhesive property (made of plastic)stain-proofing property, (to fluorine-containing resin), transparencyoccurrence of staining Others Weather resistance, Insufficient adhesiveproperty stain-proofing property (to fluorine-containing resin),transparency Occurrence of staining Outer wall material, Panel (woodenpanel for building) Weather resistance, Insufficient adhesive propertyroofing material stain-proofing property, (to fluorine-containingresin), (made of wood) transparency occurrence of staining waterresistance Window flame (made of wood) Weather resistance, Insufficientadhesive property stain-proofing property, (to fluorine-containingresin), transparency occurrence of staining water resistance Woodenbuilding material produced Stain-proofing property, Insufficientadhesive property by adhering an elastic rubber clear surface pattern(to fluorine-containing resin), material onto a back surface(transparency), Occurrence of staining of plywood water resistanceDecorative panel (wooden material) Stain-proofing property, Insufficientadhesive property clear surface pattern (to fluorine-containing resin),(transparency), occurrence of staining Others water resistance Weatherresistance, Insufficient adhesive property stain-proofing property (tofluorine-containing resin), Occurrence of staining Building FurnitureMetal furniture Stain-proofing property, Insufficient adhesive propertymaterial (fingerprint, etc.), (to fluorine-containing resin), clearsurface pattern occurrence of staining (transparency) whetherresistance(rusting) Showcase Stain-proofing property, Insufficientadhesive property (fingerprint, etc.), (to fluorine-containing resin),clear surface pattern occurrence of staining, (transparency) unclearsurface pattern Shelf plate for a chest of drawers Stain-proofingproperty, Occurrence of staining (fingerprint, etc.), clear surfacepattern (transparency) Telephone booth Telephone booth Weatherresistance, Occurrence of staining, (excluding those made of metal)Stain-proofing property, weather resistance (rusting), transparency.easy occurrence of abrasion water resistance

TABLE 12 Typical example of Example of Preferred Metal ApplyingClassification Subclassification finished product substrate polymer*oxide method Effect by polymer* Building Outer wall Ceiling panel Resin,III-VI Si, Al, Ti Coating Processability material material, roofing(excluding those made of wood (no primer required) material and metal)exterior material Door (excluding those made Resin, Processability (madeof resin) of metal) wood III, IV, V Si, Al, Ti Coating (no primerrequired), clear surface pattern Plastic panel for concrete Resin III,IV V Si, Al, Ti Coating Processability (no primer required), adhesiveproperty Gasket for building Metal Weather resistance, concrete, VI Si,Al, Ti Coating stain-proofing glass property Sun shield with a film forResin III, IV, V Si, Al, Ti Coating Processability insect proof,ultraviolet ray (no primer required), and heat ray shielding andadhesive property glass scatter prevention transparency Floor material(made of Resin III, IV, V Si, Al, Ti Coating Processability stone orvinyl chloride (no primer required), resin provided with stonetransparency pattern on its surface) Roofing material (made of ResinIII, IV, V Si, Al, Ti Coating Processability plastic with built-in solar(no primer required), system) transparency Tile (of sectional typehaving Resin III, IV, V Si, Al, Ti Coating Processability a gap, beingcapable of draining water and made of (no primer required), polyvinylchloride) transparency Synthetic resin sash Resin III, IV, V Si, Al, TiCoating Processability (no primer required), transparency Building Outerwall Decorative panel (made of Resin III, IV, V Si, Al, Ti CoatingProcessability material material, roofing thermosetting polymer alloy(no primer required), material and and used for counter, furniture,transparency, exterior material door sill, wall panel, baseboard clearsurface pattern (made of resin) for back splash, bath room and showerroom walls and wainscot) Lavatory assembly set Resin Processability(made of plastic) artificial II, III, IV, V Si, Al, Ti Coating (noprimer required), marble transparency, adhesive property Others Resin,Processability III, IV, V Si, Al, Ti Coating wood (no primer required)Outer wall Panel Wood III, IV, V Si, Al, Ti Coating Processabilitymaterial, (wooden panel for building) (no primer required), roofingmaterial adhesive property (made of wood) Window frame (made of wood)Wood III, IV, V Si, Al, Ti Coating Processability (no primer required),adhesive property Wooden building material Wood III, IV, V Si, Al, TiCoating Processability produced by adhering an elastic (no primerrequired), rubber material onto a back adhesive property surface ofplywood Decorative panel Wood III, IV, V Si, Al, Ti CoatingProcessability (wooden material) (no primer required), adhesive propertyOthers Wood III, IV, V Si, Al, Ti Coating Processability (no primerrequired) Building Furniture Metal furniture Metal II, III, Si, Al, TiCoating Processability material IV, V (no primer required), clearsurface pattern Showcase Glass, Processability wood, II, III, IV, V Si,Al, Ti Coating (no primer required), metal transparency Shelf plate fora chest of Wood III, IV, V Si, Al, Ti Coating drawers Telephone boothMetal, (excluding those made of metal) glass, resin, II, III, IV, V Si,Al, Ti Coating wood *Fluorine-containing ethylenic polymer havingfunctional group of the present invention

TABLE 13 Classification Sub-classification Typical example of finishedproduct Similar application Application Building Outer wall Ceilingpanel Floor panel (excluding those made of Medium- or material material,roofing (excluding those made of metal) metal) high-storied buildings,material, exterior Door Grating (excluding those made of metal) houses,etc. material (made of (excluding those made of metal) Trough (excludingthose made of metal) resin) Blind (excluding those made of metal) Blindfor indoor use (excluding those made of metal, paper and fabric) Blind(excluding those made of metal for outdoor use) Plastic panel forconcrete Building and houses Gasket for building Building and houses Sunshield with a film for insect Curtain with a film for insect proof,Building and houses proof, ultraviolet ray and heat ray ultraviolet rayand heat ray shielding and shielding and glass scatter glass scatteringprevention prevention Sun shield with a film for insect proof,ultraviolet ray and heat ray shielding and glass scattering preventionFloor material (made of stone or Building and houses vinyl chlorideresin provided with stone pattern on its surface Roofing material (madeof plastic Building and houses with built-in solar system) Tile (ofsectional type having a gap, Buildings and houses, being capable ofdraining water and floor of bath room or made of polyvinyl chloride)lavatory, floor of veranda Synthetic resin sash Medium-storiedbuildings, houses, etc. Building Outer wall Decorative panel (made ofSurface material material, roofing thermosetting polymer alloy andmaterial, exterior used for counter, furniture, door material (made ofsill, wall panel, baseboard for back resin) splash, bathroom and showerroom walls and wainscot) Lavatory assembly kit Assembly set (excludingmade of metal) Surface (made of plastic) (shower room) Toilet roomassembly set Toilet room assembly set (made of plastic) Prefabricatedtoilet assembly set (excluding those made of metal) (transferable type)Prefabricated public toilet assembly set (excluding those made of metal)Others Assembly set (excluding those made of metal)(sauna room) Assemblyset (excluding those made of metal)(garage) Building Outer wall Board(wooden board for building) Timber for producing domestic furnitureBuilding and houses material material, Veneer roofing material, Woodenpanel (made of woods) Window frame (made of wood) Wooden fence Buildingand houses Wooden door for indoor use Wooden building material producedBuilding and houses by adhering an elastic rubber material onto a backsurface of plywood Decorated plate (wooden material) Building and housesOthers Assembly set (wooden structure) Building and houses FurnitureMetal furniture Surface Display cabinet Glass display cabinet, wagon,display Surface, glass surface wagon, display panel, display stand, mealtransporting wagon, flower stand Shelf plate for a chest of drawersShelf, screen, desk, sofa Telephone booth Telephone booth (made ofmetal) (excluding those made of metal)

TABLE 14 Typical example of Classification Sub-classification finishedproduct Characteristics needed Defects of prior art Appliances Gas ovenwith grill Ventilation hood Stain-proofing property Insufficientadhesive property for kitchen hood for range (non-sticking property for(to fluorine-containing resin), stained oil) occurrence of stainingHousing Coordinated kitchen Range for kitchen Heat resistance,Insufficient adhesive property facilities and units (oven)stain-proofing property (oil, scorch), (to fluorine-containing resin),apparatus non-sticking property occurrence of staining Sink Heatresistance, stain-proofing property (oil), non-sticking property Waterheater Heat resistance, stain-proofing Occurrence of staining property(oil) Washstand Washstand Stain-proofing property (fur), Occurrence ofstaining, clear surface pattern poor transparency, (transparency) lowabrasion resistance Lavatory Toilet bowl Stain-proofing property,Occurrence of staining, clear surface pattern poor transparency,(transparency) low abrasion resistance Toilet stool Stain-proofingproperty, Occurrence of staining, clear surface pattern poortransparency (transparency) Water tank for Stain-proofing property(fur), Occurrence of staining lavatory clear surface pattern(transparency) Housing Bathroom, Lining for bathroom Heat resistance,Occurrence of staining, facilities and Bathroom furniture stain-proofingproperty (fur), poor transparency apparatuses transparency, (clearsurface pattern) Bath tub Heat resistance, Hot water resistance,stain-proofing property (fur), occurrence of staining, transparency poortransparency, (clear surface pattern) low abrasion resistance Handle forbath tub, Stain-proofing property (fur), Occurrence of staining, soapholder clear surface pattern (transparency) poor transparency OthersEscalator Stain-proofing property, Occurrence of staining, clear surfacepattern low weather resistance, (transparency), unclear surface patternsliding property Elevator Stain-proofing property Occurrence ofstaining, (fingerprint, etc.), clear surface pattern unclear surfacepattern (transparency), rust prevention Construction Sign Metal roadsign Weather resistance, Occurrence of staining, stain-proofing property(dust, exhaust gas), poor transparency transparency Signal Luminous andWeather resistance, Occurrence of staining, mechanical signalstain-proofing property (dust, exhaust gas), poor transparencytransparency Guardrail Metal guardrail Weather resistance, Occurrence ofstaining stain-proofing property (dust, exhaust gas), transparencyUtility pole Metal utility pole Weather resistance, Occurrence ofstaining stain-proofing property (dust, exhaust gas), transparencySound-proof wall Sound-proof wall Weather resistance, Occurrence ofstaining, stain-proofing property (dust, exhaust gas), Transparencybecomes transparency poor Others Plastic structure for Mold releaseproperty Poor mold release building and property construction

TABLE 15 Typical example of Example of Preferred Metal ApplyingClassification Sub-classification finished product substrate polymer*oxide method Effect by polymer* Appliances Gas oven Ventilation hoodMetal, Processability for kitchen with grill, aluminum, (no primerrequired), hood for range SUS, I-III Si, Al, Ti Coating adhesiveproperty steel plate Housing Coordinated Range for kitchen Metal,Processability facilities and kitchen units (oven) (no primer required),apparatuses I-III Si, Al, Ti Coating adhesive property, abrasionresistance Sink Metal, I-III Si, Al, Ti Coating Processability SUS (noprimer required), clear surface pattern Water heater Metal, I-III Si,Al, Ti Coating Processability steel plate (no primer required), clearsurface pattern Washstand Washstand Pottery, Processability artificialtransparency, resin, I-III Si, Al, Ti Coating (no primer required),marble abrasion resistance Lavatory Toilet bowl Pottery, Processabilityresin (no primer required), I-III Si, Al, Ti Coating transparency,abrasion resistance Toilet stool Resin I-III Si, Al, Ti CoatingProcessability (no primer required), transparency, abrasion resistanceWater tank for Pottery I-III Si, Al, Ti Coating Processability lavatory(no primer required), abrasion resistance Housing Bathroom, Lining forbathroom Resin, Processability facilities and bathroom metal, tile, (noprimer required), apparatuses furniture wood I-III Si, Al, Ti Coatingtransparency, adhesive property, abrasion resistance Bath tub Resin,Processability artificial (no primer required), marble I-III Si, Al, TiCoating transparency, abrasion resistance Handle for bath tub, Resin,I-III Si, Al, Ti Coating Processability soap holder metal (no primerrequired), transparency Others Escalator Metal, Processability SUS,I-III Si, Al, Ti Coating (no primer required), steel plate clear surfacepattern Elevator Metal, I-III Si, Al, Ti Coating Processability SUS (noprimer required), clear surface pattern Construction Sign Metal roadsign Metal, I-III Si, Al, Ti Coating Processability steel plate (noprimer required), transparency, adhesive property Signal Luminous andMetal, I-III Si, Al, Ti Coating Processability mechanical signal glass(no primer required), transparency, adhesive property Guardrail Metalguardrail Metal, Processability resin, I-III Si, Al, Ti Coating (noprimer required), polycarbonate adhesive property Utility pole Metalutility pole Metal, Processability concrete I-III Si, Al, Ti Coating (noprimer required), adhesive property Sound-proof wall Sound-proof wallMetal, Processability resin, (no primer required), polycarbonate I-IIISi,Al, Ti Coating transparency, adhesive property Others Plasticstructure for Resin I-III Si, Al, Ti Coating Adhesive property buildingand construction *Fluorine-containing ethylenic polymer havingfunctional group of the present invention

TABLE 17 Typical example of Classification Sub-classification finishedproduct Similar application Application Facilities for Gas oven withgrill, Ventilation hood Metal duct (for central heating) Inner surfacekitchen hood for range Metal duct (for ventilator and air conditioner)Housing Coordinated Range for kitchen Inner surface (metallic portion)facilities and kitchen units (oven) Inner surface of door apparatusesSink Surface Water heater Water heater (electric) Surface Water heater(gas) Water heater (instantaneous oil water heater) Washstand WashstandWashstand (wall-mounting type) Surface Dressing washstand - Hair washer(for domestic use) Washstand with hair washing function Washing bowl(for washstand) Washing bowl (with a cover) Washstand (bowl window type)Hair washing washstand Lavatory Toilet bowl Toilet bowl Surface Chamberpot (small size for car) Chamber pot (urinal) Chamber pot (withurinalyzer) Chamber pot (for little children) Toilet stool Toilet seatwith warm water washer Surface Toilet seat (warm water type) Toilet seat(with deodorization unit) Water tank for Surface, inside lavatoryHousing Bathroom, Lining for bathroom Shower room Wall surface, ceilingfacilities and bathroom furniture Domestic sauna apparatuses Sauna bath(for shop use) Bath tub Bath tub (prefabricated type) Surface Bath tub(with bubble generator) Handle for bath tub, Surface soap holder OthersEscalator Surface, prevention from being caught in machine ElevatorDomestic elevator Interior Construction Sign Metal road sign Sign (forbus stop) Surface Sign (for street) Sign panel (for road, mounted onguardrail) Signal Luminous and Surface, mechanical signal lighttransmitting surface Guardrail Metal guardrail Guardrail (excludingthose made of metal) Surface Utility pole Metal utility pole Utilitypole (excluding those made of metal) Surface Sound-proof wallSound-proof wall Surface, light transmitting surface Others Plasticstructure for Surface building and construction

EXAMPLE

The present invention is then explained by means of Preparation Exampleand Examples, but the present invention is not limited to them.

Preparation Example 1 Preparation of Aqueous Dispersion Comprising PFAHaving Hydroxyl

A 3-liter glass-lined autoclave equipped with a stirrer, valve, pressuregauge and thermometer was charged with 1,500 ml of pure water, 9.0 g ofammonium perfluorooctanoate and 60 g of paraffin. After replacing withnitrogen gas sufficiently, the autoclave was evacuated and charged with20 ml of ethane gas.

Then 1.9 g ofperfluoro-(1,1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)(formula (7)):

and 16.1 g of perfluoro(propyl vinyl ether) (PPVE) were fed into theautoclave with pressurized nitrogen, and a temperature inside the systemwas maintained at 70° C.

Pressurized tetrafluoroethylene gas (TFE) was introduced into theautoclave with stirring so that the inside pressure of the autoclavebecame 8.5 kgf/cm²G.

Then a solution prepared by dissolving 0.15 g of ammonium persulfate in5.0 g of water was added with pressurized nitrogen gas to initiate thereaction.

Since the pressure lowered with the advance of the polymerizationreaction, it was increased again to 8.5 kgf/cm²G by feedingtetrafluoroethylene gas at the time when it lowered to 7.5 kgf/cm²G.Thus the decreasing and increasing of the pressure was repeated.

With continuing supply of tetrafluoroethylene, every time when about 40g of tetrafluoroethylene gas was consumed after starting of thepolymerization, 0.96 g of the above-mentioned fluorine-containingethylenic monomer having hydroxyl (compound represented by the formula(7)) was introduced under pressure nine times (8.64 g in total) tocontinue the polymerization. At the time when about 400 g oftetrafluoroethylene gas was consumed after starting of thepolymerization, the supplying thereof was terminated and the autoclavewas cooled and the un-reacted monomer was released to give 1,978 g of abluish semi-transparent aqueous dispersion.

A concentration of the polymer in the obtained aqueous dispersion was21.1%, and a particle size measured by dynamic light scattering methodwas 97 nm.

Also a part of the obtained aqueous dispersion was sampled and subjectedto freeze coagulation, and the precipitated polymer was rinsed and driedto isolate a white solid. Components and their amounts of the obtainedpolymer which were determined through ¹⁹F-NMR and IR analyses wereTFE/PPVE/(Fluorine-containing ethylenic monomer having hydroxyl andrepresented by the formula (7))=99.2/0.3/0.5% by mole.

In infrared spectrum, characteristic absorption of —OH was observed at3,620 to 3,400 cm⁻¹.

According to DSC analysis, Tm was 313° C., and according to TGAanalysis, 1% decomposition temperature Td was 357° C. A melt low ratemeasured under conditions of preheating at 372° C. for five minutes at aload of 7 kgf/cm² by using Koka-type flow tester and nozzles of 2 mm×8mm length was 1.5 g/ 10 min.

Preparation Example 2 Preparation of Aqueous Dispersion Comprising PFAHaving Hydroxyl

The same autoclave as in Preparation Example 1 was charged with 1,500 mlof pure water, 9.0 g of ammonium perfluorooctanoate and 60 g ofparaffin. After replacing with nitrogen gas sufficiently, the autoclavewas evacuated and charged with 20 ml of ethane gas.

Then 3.6 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)(compound of the formula (7)) and 16.5 g of perfluoro(propyl vinylether) (PPVE) were fed into the autoclave with pressurized nitrogen gas,and a temperature inside the system was maintained at 70° C.

Pressurized tetrafluoroethylene (TFE) gas was introduced into theautoclave with stirring so that the inside pressure became 8.5 kgf/cm²G.

Then a solution prepared by dissolving 0.15 g of ammonium persulfate in5.0 g of water was fed with pressurized nitrogen gas to initiate thereaction.

Since the pressure lowered with the advance of the polymerizationreaction, at the time when the pressure lowered down to 7.5 kgf/cm²G, itwas increased again to 8.5 kgf/cm²G with tetrafluoroethylene gas, andthe decreasing and increasing of the pressure were repeated.

With continuing supply of tetrafluoroethylene, every time when 40 g oftetrafluoroethylene gas was consumed after starting of thepolymerization, 1.8 g of the fluorine-containing ethylenic monomerhaving hydroxyl (compound represented by the formula (7)) was introducednine times (16.2 g in total) under pressure to continue thepolymerization. When 400 g of tetrafluoroethylene was consumed afterstarting of the polymerization, the supplying thereof was terminated.The autoclave was cooled and the un-reacted monomer was released to give1,997 g of an aqueous dispersion. A concentration of the polymer in theobtained aqueous dispersion was 22.1% and a particle size thereof was141 nm.

A part of the aqueous dispersion was sampled, and a white solid wasisolated in the same manner as in Preparation Example 1.

Analysis of the obtained white solid indicates:TFE/PPVE/(Fluorine-containing monomer having hydroxyl and represented bythe formula (7))=98.2/0.7/1.1% by mole

Tm=314° C.

1% Thermal decomposition temperature Td=366° C.

Melt flow rate: 1.3 g/10 min

In infrared spectrum, characteristic absorption of —OH was observed at3,620 to 3,400 cm⁻¹.

Preparation Example 3 Preparation of Aqueous Dispersion Comprising PFAHaving Hydroxyl

The same autoclave as in Preparation Example 1 was charged with 1,500 mlof pure water, 9.0 g of ammonium perfluorooctanoate and 60 g ofparaffin. After replacing with nitrogen gas sufficiently, the autoclavewas evacuated and charged with 20 ml of ethane gas.

Then 3.6 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)(compound of the formula (7)) and 18.4 g of perfluoro(propyl vinylether) (PPVE) were fed into the autoclave with pressurized nitrogen gas,and a temperature inside the system was maintained at 70° C.

Pressurized tetrafluoroethylene (TFE) gas was introduced into theautoclave with stirring so that the inside pressure became 8.5 kgf/cm²G.

Then a solution prepared by dissolving 0.15 g of ammonium persulfate in5.0 g of water was fed with pressurized nitrogen to initiate thereaction.

Since the pressure lowered with the advance of the polymerizationreaction, at the time when the pressure lowered down to 7.5 kgf/cm²G, itwas increased again to 8.5 kgf/cm²G, and the decreasing and increasingof the pressure were repeated.

With continuing supply of tetrafluoroethylene, every time when 40 g oftetrafluoroethylene gas was consumed after starting of thepolymerization, 3.6 g of the fluorine-containing ethylenic monomerhaving hydroxyl (compound represented by the formula (7)) was introducednine times (32.4 g in total) under pressure to continue thepolymerization. When 400 g of tetrafluoroethylene was consumed afterstarting of the polymerization, the supplying thereof was terminated.The autoclave was cooled and the un-reacted monomer was released to give1,988 g of an aqueous dispersion. A concentration of the polymer in theobtained aqueous dispersion was 22.3% and a particle size thereof was 85nm.

A part of the aqueous dispersion was sampled, and a white solid wasisolated in the same manner as in Preparation Example 1.

Analysis of the obtained white solid indicates:TFE/PPVE/(Fluorine-containing monomer having hydroxyl and represented bythe formula (7))=97.3/0.9/1.8% by mole

Tm=314° C.

1% Thermal decomposition temperature Td=371° C.

Melt flow rate: 1.1 g/10 min

In infrared spectrum, characteristic absorption of —OH was observed at3,620 to 3,400 cm⁻¹.

Preparation Example 4 Synthesis of Aqueous Dispersion of PFA Having NoFunctional Group

Emulsion polymerization was carried out in the same manner as inPreparation Example 1 except that paraffin andperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)(compound of the formula (7)) were not used, and 1,922 g of an aqueousdispersion of PFA having no functional group was obtained.

A concentration of the polymer in the aqueous dispersion was 21.6%, anda particle size thereof was 156 nm.

A white solid was isolated and analyzed in the same manner as inPreparation Example 1.

TFE/PPVE=99.3/0.7% by mole

Tm=317° C.

1% Thermal decomposition temperature Td=479° C.

Melt flow rate: 19.2 g/10 min

In infrared spectrum, no characteristic absorption of —OH was observed.

Example 1

(1) Preparation of metal oxide sol

A 500 ml beaker was charged with 54 g of tetraethoxysilane, 46 g oftriethoxymethylsilane and 200 g of ethanol, followed by stirring at roomtemperature for one hour. Then 50 g of 0.1 N hydrochloric acid wasadded, followed by stirring at 50° C. for three hours to give a silicasol solution.

(2) Preparation of coating solution

To 44.8 g of the PFA dispersion obtained in Preparation Example 3 wasadded 87.5 g of the silica sol solution obtained in above (1), followedby stirring at room temperature for one hour to give a coating solution.

(3) Coating

On a Pyrex glass plate was applied the coating solution obtained inabove (2) by using a 10 mil applicator to form a wet coating film.

(4) Baking

After the wet coating film obtained in above (3) was air-dried at roomtemperature to dry water and ethanol on the glass substrate, followed bybaking in the air at 250° C. for 60 minutes to give an about 6 μm thickcoating film.

(5) Test

With respect to the coating solution and coating film obtained inExample 1, the following tests were carried out.

{circle around (1)} Dispersion stability of coating solution

The coating solution obtained in above (2) was allowed to stand at roomtemperature for three hours to observe dispersion stability. When thewhole solution was transparent or semi-transparent, it was evaluated as“◯”; when the whole solution was turbid in white, it was evaluated as“Δ”; and when the fluorine-containing polymer was partly precipitated inthe solution or when the whole solution was coagulated, it was evaluatedas “X”.

{circle around (2)} Transparency of coating film

To determine transparency of the coating film obtained in above (4),haze value was measured with a haze meter.

{circle around (3)} Hardness of coating film

Pencil scratch test was carried out according to JIS K5401 at roomtemperature to measure hardness of pencil.

{circle around (4)} Adhesive property

According to JIS K5400, a hundred squares were cut by cross-cutting thecoating film surface, an adhesive tape was stuck to the cross-cutsurface and the adhesive tape was strongly pulled up in the directionvertical to the surface to observe state of peeling of the cut squares.The adhesive property is indicated by the number of remaining squaresper 100.

{circle around (5)} Test for non-sticking property

Measurement was carried out at room temperature. FIG. 1 shows adiagrammatic perspective view of a test piece used for the test fornon-sticking property. The test piece 1 was one obtained in above (4),and its length a was not less than 150 mm. Stains on the test piece waswiped off with acetone. Firstly 18 mm wide adhesive tape 2 (JIS Z 1522)was cut to a length of 300 mm. Only a portion of the adhesive tape whichis 150 mm length a was put on the test piece 1, and the tape 2 wasrubbed with an eraser of JIS S 6050 to give an adhered part 3. To theremaining 150 mm long portion was stuck a paper (not shown in FIG. 1) tomake handling easy. After pressing the tape on the test piece, it wasallowed to stand for 20 minutes to well adhere the tape 2 to the testpiece 1. Then the tape 2 was peeled off only by width b (25 mm) from theend of the test piece 1, and the test piece 1 was mounted on a clamp ata lower part of a tension tester. One end of the partly peeled tape 2was folded at an angle of 180°, and set on a clamp at an upper part ofthe tester so that the tape 2 could be peeled off straightly. A forcefor peeling the tape 2 from the test piece 1 at a tension speed of 20mm/min was measured. A measured value was determined by averaging aforce for peeling the tape 2 smoothly.

{circle around (6)} Water repellency of coating film

A contact angle of water on the above-mentioned coating film wasmeasured with a contact angle meter.

{circle around (7)} Abrasion resistance test

The above-mentioned coating film was rubbed 3,000 times with a flannelcloth (cotton No. 300) at a load of 1.5 kg/4 cm², and then a contactangle of water was measured in the same manner as in above {circlearound (6)}.

The results are shown in Table 18.

Example 2

A coating solution comprising components in amounts shown in Table 18was prepared in the same manner as in Example 1 by using the aqueousdispersion of the fluorine-containing polymer (A) obtained inPreparation Example 2.

Coating, baking and tests were carried out in the same manner as inExample 1 except that the obtained coating solution was coated by usinga 6 mil applicator. The results are shown in Table 18.

Example 3

Preparation of a coating solution, coating, baking and tests werecarried out in the same manner as in Example 2 except that the aqueousdispersion of the fluorine-containing polymer (A) obtained inPreparation Example 1 was used and a coating solution comprisingcomponents in amounts shown in Table 18 was prepared. The results areshown in Table 18.

Comparative Example 1

Preparation of a coating solution, coating, baking and tests werecarried out in the same manner as in Example 1 except that the aqueousdispersion of the fluorine-containing polymer having no functional groupand obtained in Preparation Example 4 was used and a coating solutioncomprising components in amounts shown in Table 18 was prepared. Theresults are shown in Table 18.

Comparative Example 2

Coating, baking and evaluation were carried out in the same manner as inExample 1 by using only a silica sol solution to which no aqueousdispersion of fluorine-containing polymer had been added. The resultsare shown in Table 18.

TABLE 18 EXAMPLE Comparative Example 1 2 3 1 2 Aqueous dispersion offluorine-containing copolymer Prep. Ex. 3 Prep. Ex. 2 Prep. Ex. 1 Prep.Ex. 4 — Coating solution Dispersion of fluorine-containing copolymer (g)  44.8   45.2   47.1   46.2 — Silica sol solution (g)   87.5   87.5  34.0   87.5 — Dispersion stability of coating solution ◯ ◯ ◯ Δ-X ◯Components in coating film (% by weight) Fluorine-containing copolymer 54 54 75 54 — Silica  46 46 25 46 100 Coating thickness (μm)  6  3  3 6  5 Transparency of coating film Haze value (%)    0.07   0.1   3.6 20   0.05 Hardness of coating film 6H — — 6B — Adhesive property 100/100100/100 100/100 20/100 — Non-sticking property (gf/18 mm) 240 245  230 Peeled 300 Water repellency of coating film Contact angle of water(degree) 110 105  110  90  73 Abrasion resistance of coating filmContact angle of water after abrasion test (degree)  88 80 96 51  34

As is clear from the results shown in Table 18, it is seen that thecoating composition of the present invention is excellent in dispersionstability and the coating film obtained from the composition isexcellent in transparency, water repellency and abrasion resistance.

Example 4

Preparation of a coating solution, coating and baking were carried outin the same manner as in Example 1 except that instead of the Pyrexglass sheet, a 1.5 mm thick pure aluminum sheet (AlO5OP) degreased withacetone was used, to form a coating film on the aluminum sheet. Theobtained coating film was transparent and excellent in property forexhibiting clear surface pattern, and the aluminum surface was seenvividly.

By using the coated sheet, measurement of a coating thickness and testsfor adhesive property, non-sticking property and water repellency werecarried out in the same manner as in Example 1. Further tests forstain-proofing property and weather resistance were carried out by themethods mentioned below.

{circle around (8)} Test for stain-proofness for carbon

(Preparation of carbon solution)

To 90 g of ion-exchanged water was added 10 g of a carbon powder (MA100available from Mitsubishi Chemical Co., Ltd.), followed by dispersingand mixing by using glass beads to give a carbon dispersion.

(Application of carbon)

The above-mentioned carbon dispersion was applied to the coated sheet byspraying at about 50 g/m² and heated at 80° C. for two hours to give ablack test piece.

(Evaluation)

The obtained black test piece was exposed to flowing water and cleanedwith brush. Then a degree of contamination was observed with naked eyesand evaluated under the following criteria. The results are shown inTable 19.

◯: It is possible to remove contamination by washing. Nearly the samecoated sheet as before the coating of carbon dispersion is recovered.

Δ: A part of contamination could be removed by washing, but greycontamination remained over the whole surface of the coated sheet andcould not be removed.

X: Black contamination remained over the whole surface of the coatedsheet and could not be removed even by cleaning with water.

{circle around (9)} Weather resistance test

The above-mentioned coated sheet was put in I-SUPER UV tester (availablefrom Iwasaki Denki Co., Ltd.), and accelerated weather resistance testwas carried out. After 500-hour test, a contact angle of water on thecoated sheet was measured. The results are shown in Table 19.

Comparative Example 3

After 80 to 120 mesh sand blasting of the same aluminum sheet as inExample 4, a primer (POLYFLON TFE ENAMEL EK-1959 DGN available fromDaikin Industries, Ltd.) was spray-coated thereon and dried at 90° C. inan infrared drying oven to form a primer layer.

After electrostatic coating of a PFA powder coating (NEOFLON powdercoating ACX-31 available from Daikin Industries, Ltd.) on the primerlayer, baking was carried out at 350° C. for 30 minutes to give a coatedsheet having a PFA powder coating layer. A coating film having a grayishbrown primer layer was obtained.

Also the same tests as in Example 4 were carried out by using the coatedsheet having the PFA powder coating film. The results are shown in Table19.

Comparative Example 4

A paint for clear coating was prepared by mixing 100 g of ZEFFLE GK510(available from Daikin Industries, Ltd., OH value: 60) which is avarnish for room temperature curing type fluorine-containing resincoating, 10.5 g of CORONATE HX (available from Nippon Polyurethane Co.,Ltd.) which is an isocyanate curing agent and 120 g of butyl acetate andthen adjusting OH/NCO ratio to 1:1.

After spray-coating of the paint for clear coating on an aluminum sheetwhich had been sand-blasted in the same manner as in Comparative Example3, baking was carried out at 120° C. for 30 minutes to give a coatedsheet having a coating film thereon. Also the same tests as in Example 4were carried out by using the coated sheet. The results are shown inTable 19.

Comparative Example 5

A paint was prepared by mixing 100 g of ACRYDIC A801 (available from DaiNippon Ink Co., Ltd., OH value: 100) which is a varnish for a roomtemperature curing acrylic resin coating, 17 g of CORONATE HX (same asin Comparative Example 4) which is an isocyanate curing agent and 120 gof butyl acetate and then adjusting OH/NCO ratio to 1:1. The obtainedcoating was spray-coated on an aluminum sheet and baked in the samemanner as in Comparative Example 4 to give a coated sheet having acoating film thereon.

Also the same tests were carried out in the same manner as in Example 4by using the coated sheet. The results are shown in Table 19.

TABLE 19 Ex. 4 Com. Ex. 3 Com. Ex. 4 Com. Ex. 5 Appearance of coatingfilm Transparent Grayish brown Transparent Transparency Coatingthickness (μm)  7  50 20 20 Hardness of coating film 7H H H H Adhesiveproperty 100/100 100/100 100/100 100/100 Non-sticking property (gf/18mm) 235 230 Water repellency of coating film Contact angle of water(degree) 115 102 92 80 Evaluation in test of stain-proofing property forcarbon ◯ — Δ Δ Contact angle of water in weather resistance test 100 —85 not more than 20

INDUSTRIAL APPLICABILITY

The present inventors have found the following effects with respect tothe coating composition of the present invention which is obtained byintroducing the above-mentioned specific functional group into afluorine-containing polymer and combining the polymer with a metal oxideand solvent, and a coating film and multi-functional composite materialwhich are obtained by using the coating composition.

{circle around (1)} A fluorine-containing resin is inherently low inaffinity with water and solvent, and even in a dispersion offluorine-containing resin particles containing an emulsifying agent, inmany cases, the fluorine-containing resin, when added to a solvent,becomes unstable and is precipitated. However as mentioned above, byintroducing the specific functional group, dispersion stability of thefluorine-containing polymer (A) dispersion is enhanced and the stablecomposition which is free from precipitation even in combination usewith such an alcohol solvent as used in the coating composition of thepresent invention can be obtained.

{circle around (2)} Also in preparing the solution of the metal oxidesol (B-1) and in the polycondensation reaction after the hydrolysis, thefunctional group of the fluorine-containing polymer (A) partly takespart in a reaction with a metal compound or metal oxide to enhancedispersion stability of the fluorine-containing polymer (A) in thecoating composition.

{circle around (3)} In the process for further advancing thepolycondensation of the metal oxide (B) in the baking step after thecoating, the same reaction as in above {circle around (2)} occurs, andby the resulting binding, dispersibility and interfacial adhesion of thefluorine-containing polymer (A) with the metal oxide (B) (gel) in thecoating film are improved.

By the above-mentioned effects, the coating composition of the presentinvention comprising the fluorine-containing polymer (A), metal oxide(B) and solvent (C) and the coating film of the composition give, to themulti-functional composite material produced by forming the coating filmon various substrates, excellent transparency and abrasion resistanceand further water repellency, stain-proofing property, non-stickingproperty, sliding property, weather resistance and heat resistance.

Further the coating composition of the present invention can be appliedto various substrates of not only glass but also metal, resin, ceramic,etc., and can give the coating film having excellent adhesive property.The coating composition can give to various substrates not only waterrepellency and transparency but also heat resistance, weatherresistance, stain-proofing property, chemical resistance, low frictionproperty, non-sticking property, low refraction property,anti-reflection property, etc., and can be used for variousapplications.

Particularly when the substrate is glass, transparency of the substrateglass is not lost and water repellency, oil repellency, anti-reflectionproperty, low refraction property, etc. can be given to a surface of thesubstrate glass. The glass substrate coated with the coating compositioncan be used for {circle around (1)} glass for cars, {circle around (2)}glass for building, {circle around (3)} optics-related parts, {circlearound (4)} liquid crystal-related parts, etc. Also corrosionresistance, rust-preventive property, chemical resistance, weatherresistance, non-sticking property and sliding property can be given tometallic surfaces of aluminum, iron, alloy, etc., and variousapplications such as building material, chemical plant, food processing,cooking apparatus, car-related parts and office automation-related partscan be developed.

Further the multi-functional composite material of the present inventioncan be used preferably in various fields as water-repellent compositematerial, stain-proofing composite material, non-sticking compositematerial, weather resistant composite material and composite materialhaving sliding property, and particularly preferably used as a compositematerial for cooking apparatuses and for building.

What is claimed is:
 1. A coating composition comprising (A) afluorine-containing ethylenic polymer which contains afluorine-containing ethylenic recurring unit having at least one offunctional group selected from the group consisting of hydroxyl,carboxyl, a carboxylic salt group and epoxy, (B-1) a metal oxide sol,and (C) a solvent.
 2. The coating composition of claim 1, wherein thefluorine-containing polymer (A) having functional group is in the formof fine particles having an average particle size of from about 0.01 μmto about 1.0 μm.
 3. A coating film of metal oxide which comprises ametal oxide (B) and the fine particles of the fluorine-containingpolymer (A) having functional group of claim 2; said fine particlesbeing dispersed in the coating film.
 4. In the method for producing acoating film by using a metal oxide sol (B-1) obtained from at least oneselected from the group consisting of a metal alkoxide, a metalacetylacetate, a metal carboxylate, a metal nitrate and a metal chlorideand an aqueous dispersion of fine particles of the fluorine-containingpolymer (A) having functional group of claim 2 prepared by emulsionpolymerization; said method comprising the steps of (1) preparing acoating solution by mixing the metal oxide sol (B-1) and the aqueousdispersion, (2) forming the coating film by applying the coatingsolution to a substrate, and (3) baking the coating film to obtain thefilm containing the fine particles of the fluorine-containing polymer(A) having functional group in a dispersed state.
 5. The coatingcomposition of claim 2, wherein the fine particles of thefluorine-containing polymer (A) having functional group arewater-repellent fine particles having an average particle size of fromabout 0.01 μm to about 1.0 μm.
 6. A coating film of metal oxide whichcomprises a metal oxide (B) and the water-repellent fine particles ofthe fluorine-containing polymer (A) having functional group of claim 5;said water-repellent fine particles being dispersed in the coating film.7. A coating composition comprising (A) a fluorine-containing ethylenicpolymer having at least one of functional group selected from the groupconsisting of hydroxyl, carboxyl, a carboxylic salt group and epoxy,(B-1) a metal oxide sol, and (C) a solvent; said fluorine-containingethylenic polymer (A) having functional group being obtained bycopolymerizing (a) 0.05 to 50% by mole of at least one offluorine-containing ethylenic monomers having functional group andrepresented by the formula (1): CX₂═CX¹—R_(f)—Y   (1) wherein Y is—CH₂OH, —COOH, a carboxylic salt group, a carboxylic ester group orepoxy, X and X¹ are the same or different and each is hydrogen atom orfluorine atom, R_(f) is a divalent fluorine-containing alkylene grouphaving 1 to 40 carbon atoms or a divalent fluorine-containing alkylenegroup having ether bond and 1 to 40 carbon atoms, and (b) 50 to 99.95%by mole of at least one of fluorine-containing ethylenic monomerscopolymerizable with the fluorine-containing ethylenic monomer (a)having functional group.
 8. The coating composition of claim 7, whereinthe fluorine-containing ethylenic monomer (a) having functional group isrepresented by the formula (2): CH₂═CFCF₂—R_(f) ¹—Y¹   (2) wherein Y¹ is—CH₂OH, —COOH, a carboxylic salt group, a carboxylic ester group orepoxy, R_(f) ¹ is a divalent fluorine-containing alkylene group having 1to 39 carbon atoms or OR_(f) ², in which R_(f) ² is a divalentfluorine-containing alkylene group having 1 to 39 carbon atoms or adivalent fluorine-containing alkylene group having ether group and 1 to39 carbon atoms.
 9. The coating composition of claim 7, wherein thefluorine-containing ethylenic monomer (b) is tetrafluoroethylene. 10.The coating composition of claim 7, wherein the fluorine-containingethylenic monomer (b) is a mixture of 85 to 99.7% by mole oftetrafluoroethylene and 0.3 to 15% by mole of a monomer represented bythe formula (3): CF₂═CF—R_(f) ³   (3) wherein R_(f) ³ is CF₃ or OR_(f)⁴, in which R_(f) ⁴ is a perfluoroalkyl group having 1 to 5 carbonatoms.
 11. A coating film of metal oxide which comprises a metal oxide(B) and the fluorine-containing polymer (A) having functional group ofclaim 7.